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This is to certify that the
thesis entitled

THE FATE OF SELECTED PESTICIDES
I - POTENTIAL FOR LEACHING
II - EFFECT OF COMPOSTING ON RESIDUES

presented by

Christine Vandervoort

has been accepted towards fulfillment
of the requirements for

_Masr_er_'s_ degree in _Em:mno_1_ag¥

gnaw

Majorflsssor

 

Date 5/14/71“

0-7639 MS U is an Affirmative Action/Equal Opportunity Institution

 

 

 

 

 

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THE FATE OF SELECTED PESTICIDES
APPLIED TO TURFGRASS

PART I
POTENTIAL FOR LEACHING

PART H
EFFECT OF COMPOSTING ON RESIDUES

By

Christine Vandervoort

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTERS OF SCIENCE
Department of Entomology

1995

Dr. Matthew J. Zabik

ABSTRACT

THE FATE OF SELECTED PESTICIDES
APPLIED TO TURFGRASS

PART I
POTENTIAL FOR LEACHIN G

PART II
EFFECT OF COMPOSTING ON RESIDUES

Christine Vandervoort

ABSTRACT

THE FATE OF SELECTED PESTICIDES APPLIED TO TURFGRASS
PART I-POTENTIAL FOR LEACHIN G
PART II-EFFECT OF COMPOSTING ON RESIDUES
By
Christine Vandervoort

Applications of select pesticides to turfgrass were made and their fate in an
intact soil monolith lysirneter and composted turfgrass system were studied.
Detection of the parent molecule applied to each system was the end point for
determination of the fate within the system.

In the lysirneter system chlorothalonil, triadimefon, dicamba, 2,4-D, isazofos,
fenarimol, metalaxyl, and propiconazole were applied to turfgrass. The water
collected from lysirneter was analyzed over 28 months time. Triadimefon was the
only pesticide recovered from the lysirneter leachate.

The composted turfgrass had isoxaben, chlorpyrifos, 2,4-D, clopyralid,
triclopyr, and flurprimidol sprayed on to established turfgrass. The grass was clipped
one day after application and put in compost piles. The compost piles were sampled
for 365 days after application of the pesticides and analyzed. The results showed
declining residues of pesticides over time. The data suggest a biphasic rate of loss.

The lysirneter system showed the parent compound was not coming through

the lysirneter at sufficient concentration to be detected by the method. The compost

clearly showed signs of decline in the concentrations of the applied pesticides.

ACKNOWLEDGEMENTS

I wish to thank Dr. Matthew J. Zabik, who is the chairman of my Masters of
Science degree committee, for his inspiration, confidence in me, guidance and
technical expertise.

I also extend my gratitude and appreciation to Dr. L. Patrick Hart, Dr. Suzanne
M. Thiem, and Dr. Larry G. Olsen for the guidance and excellent courses offered to
me.

I give thanks for the co-workers in Dr. Matthew J. Zabik laboratory, especially
to Matthew D. Siler, Glenn A. Dickmann, and Jie Wang who helped in so many ways.

I want to give special thanks to my husband, Richard Othoudt, my children
Laurel, Natalie, Matthew, and Sophie, and my parents Robert B. Vandervoort and

Thelma B. Vandervoort for their patience and love.

iv

TABLE OF CONTENTS

 

SECTION flA_G_E
LIST OF TABLES ....................................................................................... vii
LIST OF FIGURES .................................................................................... viii
LIST OF APPENDICES ................................................................................ x
INTRODUCTION ......................................................................................... 1
OBJECTIVES ............................................................................................... 2
LITERATURE REVIEW ............................................................................. 10
PART I - POTENTIAL FOR LEACHING ......................................... 10
PART H - EFFECT OF COMPOSTING ............................................ 12
PESTICIDE FATE IN THE ENVIRONMENT .................................. 12

ADSORPTION AND PARTITIONING TO THE

ENVIRONMENTAL MEDIA ...................................... 12
VOLATILITY ......................................................................... 14
DIFFUSION AND FLOW ...................................................... 15
PHOTOCHEMISTRY ............................................................ l7
BIOCHEMICAL DEGRADATION ........................................ 23

V

CHEMICAL DEGRADATION .............................................. 23

EXPERIMENTAL DESIGN ........................................................................ 26
PART 1 - POTENTIAL FOR LEACHNG ........................................ 26
PART II - EFFECT OF COMPOSTING ON RESIDUES ................... 29
ANALYTICAL METHODS .......................................................................... 32
STANDARD PURITY ....................................................................... 32
PART 1 - POTENTIAL FOR LEACHIN G ......................................... 32
PART II - EFFECT OF COMPOSTING ON RESIDUES ................... 39
RESULTS AND CONCLUSIONS ................................................................ 45
PART I - POTENTIAL FOR LEACHIN G .......................................... 45
PART H - EFFECT OF COMPOSTING ON RESIDUES .................. 51
CONCLUSIONS ............................................................................... 67
APPENDICES .............................................................................................. 69
APPENDD( A - DATA ANALYSIS OF COMPOST SAMPLES ........ 69
APPENDIX B--WATER LYSIMETER DATA .................................. 72
APPENDD( C--STANDARD OPERATING PROCEDURES ............. 96
LIST OF REFERENCES ............................................................................. 113

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

LIST OF TABLES

Weed pests that impact golf courses ............................... 6
Insects pests that impact golf courses ............................. 7

Disease/Pathogens that impact golf courses .................... 8
Nematodes that impact golf courses ............................... 9

Average bond energies .................................................. 21
Pesticide Lysimeter Application Schedule ..................... 28
Physio-chemical Properties of the Test Chemicals ........ 31
Standard Purity ............................................................. 32
F irst-Order Decay Constants ......................................... 65

vii

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11
Figure 12
Figure 13
Figure 14
Figure 15

Figure 16

LIST OF FIGURES

Photochemical pathways ....................................... 22
Phenylureas structure ............................................ 25
Phenoxyalkanoic acid structure ............................. 25
Pesticide structures ................................................ 33
Pesticide structures ................................................ 34
Chlorpyrifos normalized inside .............................. 53
Chlorpyrifos normalized outside ............................ 54
Triclopyr normalized inside ................................... 55
Triclopyr normalized outside ................................. 56
Isoxaben normalized inside .................................... 57
Isoxaben normalized outside .................................. 58
Flurprimidol normalized inside .............................. 59
Flurprimidol normalized outside ............................ 60
2,4-D normalized inside ......................................... 61
2,4-D normalized outside ....................................... 62
Clopyralid normalized inside ................................. 63

viii

Figure 17 Clopyralid normalized outside ............................... 64

ix

LIST OF APPENDICES

APPENDIX A--TURFGRASS COMPOST DATA

Table Al-Chlorpyrifos Concentration .............................................. 69
Table A2-Triclopyr Concentration .................. . .................................... 69
Table A3-Isoxaben Concentration ....................................................... 70
Table A4-Flurprimidol Concentration ................................................. 70
Table A5-2,4-D Concentration ........................................................... 71
Table A6-Clopyralid Concentration ..................................................... 71

APPENDIX B--WATER LYSIMETER DATA

Table BO-Sample Dates for Water Collection ................................. 72
Table B l-Triadimefon Concentration .................................................. 73
Table B2-Isazophos Concentration ...................................................... 75
Table B3-Fenarimol Concentration ..................................................... 77
Table B4-Propiconazole Concentration ............................................... 79
Table B5-Chlorothalonil Concentration ............................................... 81
Table B6-2,4-D Concentration ............................................................ 85
Table B7-Dicamba Concentration ....................................................... 87

X

Table B8-Metalaxyl Concentration ...................................................... 89

Table B9-Rainfall and Irrigation Data ................................................ 93
Table B IO-Voltune of Water Collected ............................................... 94
APPENDIX C--STANDARD OPERATING PROCEDURES .............................. 96

INTRODUCTION

The objective of this research is to assess the potential for contamination of
ground water, soil, and other non-target areas by pesticides used on turfgrass. The
use of pesticides has become an integral part of man's desire to increase production
of food and fiber. The entry of pesticides into the atmosphere, aquatic, and biological
components of the environment provides the potential for chronic risk to the
environment and human health. An understanding of the physio-chemical properties
of the pesticide and the factors controlling them in the environment will permit
assessment of possible risk. Groundwater is a finite and valuable resource that
provides the United States with 51 % of its drinking water (Coutu, 1989) and 43 %
of Michigan residents rely on grormdwater for drinking. The rate at which pesticides
disperse or degrade may impact surface water and aquatic life forms. Pesticides with
high octanol-water partition coefficient tend to accumulate in hydrophobic
compartments (biota and sediments) and may adversely impact the resulting organism
(Wilcock, 1994). Aquatic organisms are immersed generally for their lifetime in
water and their exposure may be acute to chronic depending on the contaminant level
in the water. The reason for such studies is to assess non-target deposition of

contaminants, as they may bioaccumulate in the'food chain thus exposing humans

1

2

(Mathews, 1994). The insecticide DDT has a degradation product DDE which has
been attributed to causing eggshell thinning in wild birds (Giesy, 1994) and bald
eagles have had declining births and viable young which has been considered related
to causal agent such as polychlorinated diaromatic hydrocarbons. A study conducted
in 1989 in Turkey showed hexachlorobenzene (banned organochlorine pesticide) to
be found in human fat tissue, even though it was banned in 1959 (Burgaz, 1994). To
use chemical tools responsibly requires knowledge of how pesticides are
disseminated, distributed, degraded, and accumulated in the environment, this will
help to avoid similar situations in the future.

OBJECTIVES

The specific objectives of the research are to gain knowledge of the pesticides
applied to turfgrass in respect to detection of the intact pesticide leaching through a
soil filled monolith lysimeter and the effect composting of turfgrass has on parent
pesticide residues.

The lysirneter study looks at the vertical transport of the intact pesticide
through turf, thatch, and soil. Knowledge of the behavior of a pesticide in the soil
will help in the understanding of the distribution of the pesticide in the environment.
The lysirneter drainage will address the ability of a pesticide to travel with the water
through the soil profile, under various rainfall and weather events, to show how
pesicides behave under actual field conditions.

The composted turfgrass study evaluates the option of applying lawn and

3

garden wastes to growing gardens as a nutrient amendment and to help maintain the
moisture in the soil. The compost must be applied safely without phytotoxicity or
toxicity to non-target organisms due to residual pesticides. The fate of the intact
applied pesticide is measured as a end point to evaluate the toxicity to the
environment from the compost.

The population of the United States has had an extensive urban shift and this
shift has brought an array of problems. The homeowner has yard wastes that are
being placed in landfills and the landfills are of concern to the public. The State of
Michigan Law PA 264 Section 1821 (2) has now banned yard wastes being placed in
landfills. The concerns include both the vast amount of material and the nature of the
material being placed in the landfills. Large quantities of pesticides have been
applied to turfgrass and ornamental shrubs to control pests in urban areas.
Composting of yard waste brings the concern of chemical residues in the resulting
plant material. The pesticides used may follow several paths after application to the
target system. Pimental and Levitan (1986) believe less than 0.1 % of pesticides
applied reach the target organism. Relatively small areas of the world are treated with
pesticides, but universal distribution of small amounts are caused by water, wind,
food, and feed movement. Golf courses are often a casualty of many pest problems.
The average maintenance cost for a golf course is $151,000 with $13,000 being spent
on pesticides and $7,300 spent on fertilizers (Shank, 1985). The goals of turfgrass

maintenance is high quality turfgrass and reasonable economic return. Weed

4

pressures are a major concern for turfgrass systems due to the esthetic appeal being
sought. Weeds compete for nutrients and can shade out the turfgrass which makes
the turfgrass an unappealing place to golf. Turf managers make decisions to apply
herbicides routinely but insecticides and fungicides application are done on
assessment of the potential impact to the turfgrass (Commercial Turf Establishment
and Pest Management, 1993). Insect and other disease vectors cause other control
problems on the golf course. An example of an insect pest is the mole cricket, a
tunneling insect, that causes major damage to grass. A golf course with a average
infestation of mole cricket may spend up to $25,000 a year trying to hold them at a
tolerable level (Reese, 1994). To help reduce the chemical control methods, which
are only partially effective, biological controls have been used with success in North
Carolina and Florida. The mole cricket is an immigrant from South America and
when it came to North America it did not bring its natural predators. The IPM
approach has introduced red-eyed flies and entomogenous nematodes as natural
predators. The IPM program was able to show a increase in green revenues of
$250,000 per year (Reese, 1994). The economic losses are a driving force for the
need of chemical and biological control in turfgrass management. Table 1 (weed
pests), Table 2 (insect pests), Table 3 (diseases),and Table 4 (nematode pests) show
the common ttu'fgrass pests found in lawns and golf courses. Weed control in
turfgrass can be broken down into two categories, grasses and broadleaves.

Postemergence herbicides such as 2,4-D, dicamba, clopyralid, triclopyr and isoxaben

5

are commonly used for broadleaf control. The grasses may be controlled with
preemergent herbicides when germinating, but once established, the control of
perennial grasses are most difficult. The mildew, rusts, smut, and other fungal
diseases are controlled by chlorothalonil, propiconazole, fenarimol, triadiamefon, and
metalaxyl. Chlorpyrifos and isazofos are used in control of bluegrass billbug, chinch
bug, cutworms, June beetle, and sod webworm. The lawn care industry has an array
of problems, one is the public perception of an industry which relies on toxic
chemicals and a lack of concern of the environment.

Pesticides in the environment are dissipated by many mechanisms and
biological processes, which do not necessarily lead to complete degradation of the
chemical. The obvious choice would be for the pesticides to breakdown to innocuous
products. Pesticides may degrade or bind to plant material or soil components. The
compounds that bind are still of concern because of the possibility of future
bioavailability to another organism. The release of an intact pesticide or a toxic
pesticide metabolite is a real concern because of the potential damaging effects. The
rate of release may be so slow, so as to be inoffensive to the environment, or may be

rapid and cause damage.

6

Table l. Weed pests that impact golf courses

 

 

mm 591me Name
clover .............. T rifolium spp.
prostrate knotweed . . . . Polyganum aviculare
crabgrass ............ Digitaria spp.
dandelions ........... T araxacum ofiicinale
chickweed ........... Stellaria media

yellow nutsedge ......
annual bluegrass ......
goosegrass ..........

barnyardgrass ........
foxtails .............
oxalis ..............
spurge .............

ground ivy ..........

creeping Speedwell . . .

wild violets .........

Cyperus esculentus
Poa annua

Eleusine indica
Echinochloa crusgalli
Setaria spp.

Oxalis stricta

E uphorbia supina
Glechoma hederacea
Veronica filliformis

Viola spp.

.7

 

Table 2. Insect pests that impact golf courses

M Name impact

black turfgrass ataenius/Ataenius spretulus. . . . larva feed on roots

cutworms/Agriotis Ipsilon ................ worms feed on foliage

may or june beetles/Phyllophaga spp ......... larva attack roots

sod webworm/ F issicrambus mutabilis ....... lst & 2nd generation feed
on foliage

european chafer/Rhizotropus majalis ......... larva feed on roots

japanese beetle/Popilliajaponica ............ larva feed on roots

ants/Formica spp.

greenbugs/Schizaphis graminumants
chinch bug/Blissus Ieucopterus
bluegrass billbug/Schenohporus parvulus

8

Table 3. Disease/Pathogens that impact golf courses

 

Wen impact

dollar spot /Sc1erotinia hemcocarpa .................. attack cool season grasses
brown patch/Rhizoctonia solam’ ..................... attack cool season grasses
fusarium patch/Fusarium m'vale .................... attack cool season grasses
helrninithosporiurn leaf spot/Bipolaris sorokiniana ....... attack cool season grasses
melting out/Drechslera poae ...................... attack cool season grasses
pythium blight/Pythium aphanidermatum .............. attack cool season grasses
typhula blight/Tuphula incamata ..................... attack cool season grasses

take all patch/Gaeaumannomyces gaminis .................... attack bentgrasses

9

Table 4. Nematodes that impact golf courses

Warsaw impact

 

pinewood nematode/Bursathelenchus xylophilus ..... attack the genus pinus

10

LITERATURE REVIEW

To evaluate the fate of toxic chemicals, the nature of the chemical and the
environment it finds itself in must be examined. Pesticides are applied in various
ways to reach the target organism. The journey fiom the application equipment to the
target must be controlled as much as possible to minimize loss to nontarget organisms
and the environment. Pesticides usually breakdown or degrade via three methods,
photodecomposition by sunlight, biological decomposition, and/or chemical
decomposition. The rate of degradation is influenced by volatilization, surface runoff,
leaching, capillary action (moving upward in the soil profile), sorption (includes
adsorption, partitioning, and absorption), and storage in biological organisms. A
discussion of leaching potential and effect of composting on pesticides will follow,
with a look at the mechanisms effecting these fate, such as adsorption and partitioning
to the environmental media, volatility, diffusion and flow, photochemistry,
biochemical, and chemical degradation will follow.
PART I - POTENTIAL FOR LEACHING

The potential for leaching can be assessed using monolith soil filled lysimter.
Outdoor lysirneters offer a range of climatic conditions that effect the movement of
the applied pesticide. The soil in undisturbed lysirneters maintain the macro- and
micro- pores, fissures, and channels which effect the flow. Benazolin—ethyl (ring
labelled with 14C) (Leake, 1991) was applied to a lysirneter with bare soil on top,

over a 18 month period. The majority of the recovered radioactivity was in the top

ll

10 cm of the soil column. The presumed loss of radioactivity was to mineralization
of the parent pesticide. In one lysirneter no radioactivity above background was
detected and in the other less than 1 % of the total applied was detected in the
leachate. In Germany a undisturbed soil lysirneter leachatc (Kordel, 1991) was
collected over one year and then the soil cores were removed and analyzed.
Cloethocarb was applied as a radio-labeled compound and the radioactivity was
measured. The results showed less than 0.02 ug/l total radioactivity were recovered
in the leachatc throughout the year. Cloethocarb was detected down to 40 cm in the
soil profile. Bentazone (Kordel, 1991) was also applied to a young pea crop with
winter wheat as a rotational crop and less than 0.1 ug/l of total radioactivity was
recovered in two years. Betazones metabolites were detected in the leachatc but
never exceeded 0.02 ug/l. The trend of minimal residues in the leachatc occurs
commonly with lysimeters that have undisturbed soil profile where as the ones that
are laboratory filled show different results. The design facilitates leaching in that it
does not have a vegetative cover, OM from plant debris in the upper layers of soil are
missing, and the soil chosen is sand and gravel. Since the middle 19605, soil
scientists have noticed that the extent of soil uptake for nonionic organic compounds

(contaminants and pesticides) is closely related to the OM content in soil (Sun, 1992).

12

PART II - EFFECT OF COMPOSTING ON RESIDUES

Composting is the biotransforrnation of complex polysaccharides and other
organic compounds to CO2 and humic substances by microorganisms. In controlled
laboratory composting studies percent loss of carbon averaged 28.9 % +/- 9.2
(Michel, 1993) in 32 days. The same study showed 71 % loss in cellulose and 73 %
loss of hemicellulose after 43 days of composting. In another study, a leaf and grass
compost amended with 1“C ring labelled 2,4-D was analyzed for evolved CO2
(unpublished by Michel at Michigan State University). After 10 days 27 % of the 1“C
ring labelled 2,4-D was mineralized to CO2 and 50 days after composting 47 +/-6 %
was mineralized.
PESTICIDE FATE IN THE ENVIRONMENT
ADSORPTION AND PARTITIONING TO THE ENVIRONMENTAL MEDIA

The rate of pesticide applicafion to obtain adequate control often depends upon
the amount of organic material (OM) found in the soil. The OM has the ability to
form strong chemical bonds with some pesticides, but interacts with other compounds
only by van der Waals forces (weak forces). The binding of the chemical residues
may contribute to their persistence in the soil and render them harmless to the
environment (Stevenson, 1975). The nature of the pesticide binding to the OM in soil
is obscure due to the many forms of OM and its non-precise structural formula. The
humic acid and fulvic acid portion of OM is negatively charge, with high molecular

weights and diverse functional groups. They have several oxygen-containing groups

13

such as carboxyl, aliphatic, alcohols, phenolic, enolic-hydroxyls, and carbonyls.
Sulfur and nitrogen functional groups are also found in OM. OM may interact with
pesticides through several attachment schemes. The attachment mechanisms include
van der Waals force, ligand exchange, H-bonding, and hydrophobic bonding.
Sorption of pesticides to soils is correlated to the rapid increase in sorption with
decreasing pH.

Ion exchange can occur with some pesticides to the negative sites in OM or
clay, if the pesticide is positively charged or protonated. The cation exchange
capacity of soil (the concentration of negatively charged sites) will always be greater
than the pesticide concentration, except perhaps in very sandy soils. The ability of
the soil to ion exchange is pH-dependent and becomes greater for neutral and basic
soils. Anionic pesticides will generally not be attracted to the negatively charged OM
or clay unless a divalent cation is bridging between the soil and the pesticide. OM
and clay are often found bound together in a clay-metal-OM complex and the
absorbed species are found on both the clay and OM surfaces. Most pesticides have
a greater affinity to OM than the clay surfaces. When the ratio of clay to OM is the
same but different clays are involved a general rule is to have greater adsorption to
montrnorillonite, illite than kaolinite clay types. Clay surfaces have several
adsorption mechanisms such as ion exchange, coordination complexes, van der Waals
forces and H-bonding. These mechanisms are specific for the chemical and clay

mineral involved. Clay minerals generally have a high surface area and high charge

l4

density thus readily react with any molecule that has a charge or dipole (Bollag,
1990). Water will compete with chemicals for adsorption sites on clay minerals and
adsorption of a chemical may not be as great in moist soils as in dry soils (White,
1975). Multivalent adsorbed cations in clay can polarize water so that it can donate
H atoms and absorb basic pesticides. A pesticide that becomes bonded to a clay
mineral may become biologically unavailable both to organism and to degradation.
In some cases, however, adsorption can promote abiotic degradation.
Hydrolysis of sorbed molecules is slower than in the aqueous phase (Macalady,
1983). Abiotic hydrolysis products in sediment systems were found to be, in many
cases, the same as the products of hydrolysis in clear water (Macalady, 1983).
VOLATILITY

Volatilization is a function of the vapor pressure of the pesticide and is
affected by pesticide concentration, soil-water content, adsorptivity of the soil,
diffusion rate in soil, temperature, and air movement. Volatilization is most rapid
immediately following application, although it will continue over an extended period
of time, especially in a dry environment. Air currents provide for movement of
pesticides from the site of application. Particulate matter and pesticide vapors are
canied to high altitudes and for long distances. Volatilization may be minimized with
adjuvants added to the spray mixture and care in selection of weather conditions that
limit dispersal. The droplet size in spray applications must be sufficiently small as

to arrive at the target and large enough to provide enough mass to hit the target and

15

not tumult from the path. The rate of evaporation is related to pressure and

temperature by

 

where P is pressure, T is temperature, k is constant which is unit specific, and AB is
the rate of evaporation (Hartley and Graham-Bryce, 1980). The rate of evaporation
increases as temperature increases due to increased kinetic energy. Evaporation will
occur as the number of molecules with sufficiently high energy to overcome the
attractive forces of the surrounding molecules escape the liquid phase into the gaseous
phase.
DIFFUSION AND FLOW

The chemicals that do hit the target organism must then make their way to the
site of action within the organism. To transverse the various membranes to the site
of action requires molecules to pass through lipid bilayers which are generally
nonpolar. The chemical will be driven by the chemical concentration gradient to its
partition concentration ratios appropriate for the two chemicals (layers) it is
partitioning into. Adsorption of pesticides on to plant material, soils, clay, and OM
may be reversible or irreversible, although in a heterogeneous compost system the
distinction may not be clear. A compost system also, has a dynamic concentration

gradient. As the compost material is broken down, it may release a chemical of

16

interest or bind it as the cherrrical composition is always changing. Molecular
diffusion is a spontaneous process which occurs continuously while a concentration
gradient exists. Molecular diffusion is constrained only by the matter forming the
medium. Diffusion may be measured by using a principle known as Fick's
(Tchobanoglous, 1985) law or the rate of diffusion in a given direction at a point

normal to the cross sectional area. F ick's law is given by:

£1.19—
A

where F is the arnount of chemical diffusing per unit time across area A and dC/dx
is the concentration gradient in the same direction. The proportionality constant is
the diffusion coefficient, D. Although these theoretical equations exist for calculating
concentrations of cherrricals in steady-state they provide limited value in natural
systems where the concentration gradients are always changing. Diffusion in a
porous medium is orders of magnitude slower than in solutions. The pathways in soil,
plant material, and other organic systems is complicated by membranes, fats,
organelles, and various other components that make up the medium. As pesticides
move throughout the environment they encounter varying degrees of tortuosity of
pathway. Blind pores (dead end) may exist in natural porous media and these
contribute to micro rates of diffusion that deviates from the expected rate from Fick's

law. The blind pores may also become traps and allow for increased chemical load

17

to the medium. The standard method of measuring adsorption is to apply several
concentrations of a chemical in a solution to the adsorbate and measure the remaining
chemical after a known time. In a compost system the reliability of creating a
uniform system to test adsorption is in question. The compost and the lysirneter
system both have intrinsic properties that can not be reduced to allow for accurate
measurements of adsorption over time. The interplay between solute, solvent, and
adsorbate may be generalized and measured at the expense of evading the specific
factors controlling the movement of the pesticides.

Molecular diffusion will occur as long as there is a concentration gradient.
The process is not energy dependent and will occur instantaneously and continuously.
Diffusion can not dissociate from other forces such as flow. Though flow does not
effect diffusion, it does change the concentration of solutes that are subject to the
concentration gradients.
PHOTOCHEMISTRY

Many organic compounds undergo a chemical change when exposed to visible
and/or ultraviolet radiation and occurs more often when atmospheric oxygen is
present. A molecule that absorbs a quanta of radiation between 200 to 600 nm
becomes electronically excited. The excited species can be expected to differ from
the ground-state atom in reactivity. Not only does it possess a new electron

configuration but it has extra energy. The relationship between energy, E and

wavelength, 1 is given by:

18

E = 333—21 kJ mol-1

The photochemical wavelength range given above has energies similar to chemical
bond energies found in organic compounds. Table 5 shows some average bond
energies of organic compounds. The bond energy range is 140-800 kJ/mole and the
ultraviolet-visible energy range has similar energies of 200-600 kJ/mole. If the
electronic excitation energy can in some way be available for bond rupture, then
chemical change may occur. Ifthe electronic excitation is sufficient to overcome the
energy of activation, then the excited species will react more rapidly than the ground
state species.

Thermal energy may also be distributed in a molecule by translation,
rotational, and vibrational excitation. The fate of the electronically excited species
can be illustrated by Figure 1. Chemical change can occur as in pathway (i) of
Figure 1 by dissociation, a result of direct reaction with the electronically excited
species (process ii), isomerization (process iii), intermolecular energy transfer
(process iv), intrarnolecular energy transfer (process v), luminescence (process vi),
quenching (process vii), or ionization (process viii).

Photochemistry involves two processes, the process of absorption and the fate
of the electronically excited species formed. The process of absorption involves a
loss of intensity of electromagnetic radiation and the gain in energy of the absorbing

molecule. The difference in energy of the ground state molecule and the excited is

19

equivalent to one photon of radiation. The converse process occurs when an excited
state molecule gives up energy to electromagnetic radiation to increase the intensity
of the radiation field.

Spontaneous emission is the major concern in photochemistry, which includes
fluorescence and phosphorescence. Fluorescence is the emission of energy
corresponding to a transition between states of the same multiplicity (singlet-singlet
or triplet-triplet transition). In a singlet state all electrons are paired, where in a triplet
two electrons are unpaired with parallel spins. Phosphorescence occurs after a singlet
excited species releases energy via an intersystem crossing to a triplet state and the
subsequent excited triplet emits radiation down to the ground singlet state.

As indicated in Figure 1 process (i) photodissociation can further be divided
into optical dissociation, predissociation, and induced predissociation. Optical
dissociation occurs when a electronically excited species has absorbed sufficient
energy to dissociate into fragments, were predissociation occurs when an excited state
is populated below its dissociation energy limit and a radiationless intrarnolecular
energy transfer occurs which then puts the excited species into another electronic .
level above its dissociation limit and with this will dissociate to its fragments. The
new state may also be less than the dissociate energy state and not result in
dissociation. Induced predissociation becomes significant in species similar to the
predissociation but they have added perturbation such as collisions, magnetic fields,

or electric fields. These added perturbations contribute to the energy needed for

20

dissociation.

There exist two significant problems with descriptive photochemistry in large
organic molecules. The absorption spectra are complex and may not be resolvable
to determine the occurrence of optical, pre, and induced dissociation because of the
close spacing of vibrational and rotational levels and the increased number of
electronic states. The second obstacle is the multiple fragmentation pathways that
exist for an excited polyatomic molecule. Although absorption is wavelength
specific, in complex molecules fi'agrnent products may occur simultaneously.

Excited species which lead to chemical reaction include reactions such as
isomerization, intermolecular reaction, and ionization. The intrinsic reactivity of the
specific electronic arrangement, the effect of the excitation energy and the lifetime
of the particular excited state contribute to the reactivity of the excited chemical. The
intrinsic reactivity of excited state molecules have alterations in their geometry, dipole
moment, electron donating and accepting characteristic which changes their acid-
base properties. Ethene shows a geometric change from a planar molecule to a
perpendicular molecule on excitation, this occurs due to the higher energy electron
leaving the pi bond and only the sigma bond left. Perpendicular configuration allows
for minimal electrostatic repulsion of the non-bonded electrons. Dipole changes are
seen with absorption of electromagnetic radiation due to changes in distribution of

electrons.

21

TABLE 5 Average Bond Energies (kJ/mole)

 

 

 

 

 

 

 

 

 

 

 

 

(figanic Bond Bond Energy Organic Bond Bond Energy
H-H 435 N-Cl 201
H-F 565 C-C 347
H-Cl 43 l C=C 812
H-Br 364 C-H 414
F-F 155 C-0 ' 35 1
Cl-Cl 243 C=O 707
0-0 13 8 C-Cl 326
O-H 464 C-N 293
O-F 184 8-8 264
O-Cl 205 S-H 339
N-N 159 P-H 3 l8
N-H 3 89 P-Cl

 

 

 

 

 

 

22

AB'l'hV . AB++C

 

 

 

Figure 1 Photochemical Pathways

23

BIOCHEMICAL DEGRADATION

Chemicals are attacked by various anaerobic and aerobic bacteria, fungi, and
other microbes. For a chemical to be degraded it must provide an energy resource to
the attacking organism, otherwise the chemical may be enzymatically attacked as a
mechanism to detoxify the chemical from harming the microbes environment.
Though degrading organisms are ubiquitous, they may not occur in sufficient quantity
as to need to compete for the anthropogenic chemical and never use them as a energy
source, if this is the case the chemical will remain unchanged.

The composted grass is also attached by the degrading organisms, cellulose is
hydrolyzed to smaller celludextrins subunits and the major degraders of lignin are
higher fungi such as ascintcetes and basidiomycetes. There are four primary
ligninases implicated in lignin breakdown. Ligninase the primary enzyme, catalyzes
extensive oxidation of non-phenolic as well as phenolic unit in lignin. Laccase is a
extracellular enzyme produced by white-rot fungi. This oxidizes the phenol to the
phenoxy radical and transfers 4 electrons to Oz. Manganese Peroxidase functions
similar to laccase in oxidation of the phenol. Lignin degradation also requires H202,
this is provided by several different oxidases.

CHEMICAL DEGRADATION

The fate and persistence of chemicals is affected by such interrelated processes

as solubility, photochemistry, volatility, sorption to OM and soil components,

hydrolysis, and the combined actions of weathering such as wind, humidity, and

24

temperature so as to expose the chemical to breakdown. Oxidation, hydrolysis,
reduction, and conjugation precipitate molecular changes. Chemical transformation
and degradation may result in metabolites that are more toxic then the parent
compound.

The major metabolite of phosphorothioates (general structure in Figure 2) are
a hydrolysis product, 2,5,6-trichloro-2-pyridinol. The thio group is oxidized to oxon
and reduction of the chlorine and replacement with SCH3 is seen in Chlorpyrifos.
The fate of phenoxyalkanoic acids (general structure in Figure 3) degradation is by
beta oxidation to remove two of the carbon fragments from the functional end of the

alkanoic acid until only a hydroxyl is left. The ring structure is metabolized to C02.

25

Figure 2 General Structure of Phosphorothioate (Similar to Chlorpyrifos)

Cl- \ Cl

/ 0-. ..
c1 N/ o—f< 2 5
s o-——c2II5

Figure 3 General Structure of Phenoxyalkanoic Acids (Similar to 2,4-D)

OCHZCOZH

Cl

Cl

26

EXPERIMENTAL DESIGN
PART I - POTENTIAL FOR LEACHING

The objective of this study was to collect leachatc fiom four lysirneters for
analysis of applied pesticides. Installation of two lysirneters was completed in
April of 1990 at Hancock Turfgrass Research Center (HTRC) in E. Lansing, MI.
These lysirneters are termed soil monolith lysirnters to mean that they are soil
filled with a undisturbed soil core. Many researchers use soil packed lysirneters
such as a study conducted at University of Georgia Agricultural Experimental
Station in early 1991. The lysirneters constructed had gravel on the bottom,
followed by sand, and then a soil mix with turfgrass about one year old. Soil OM
and plant litter is largely responsible for the immobility of organic compounds in
agronomic areas (Boyd et al., 1990). Sand and gravel are known leachers of
organic chemicals. To make the lysirneters, a stainless steel cylinder 45 inches in
diameter and 4 feet deep was driven into the soil, using a backhoe until the
cylinder was completely filled with soil. The cylinder was then removed from the
ground and a bottom with a drain was welded on and then placed back in the
ground. The soil in the lysirneters is a Owosso sandy loam soil and Kentucky
bluegrass turf was established on the surface. The second two lysirneters were
installed in 1991 and constructed in the same manner as the earlier ones, except
for the top 18-20 inches was removed and pea gravel and sand was put on. This

was to simulate United States Golf Association greens mix as seen on the golf

27

course.
The pesticides were selected based on their use and leaching potential.
Leaching potential was evaluated by water solubility, strength of adsorption to soil
components, and half-life in soil. Pesticides with water solubilities below 10 ppm
were not expected to leach and half-lives less than 30 days were not thought to be
a problem but rather to degrade before reaching groundwater. The pesticides
were first applied to the turfgrass August 12, 1991 and the application continued
until September 4, 1992. The Application schedule is in Table 6 and it shows the
time and rate of the applications. The the water leachatc samples were collected
fiom the lysirneter about every two weeks. If the volume of water coming through
the lysirneters was large then the samples were obtained more often, to avoid loss.
Method validation studies were conducted on each chemical and taken through the
entire analytical method in triplicate. This was done by taking 100 g of distilled
water and adding a known amount (spike) of pesticide to it. The results are
isazophos 100 %, chlorothalonil 94 %, dicamba 129 %, 2,4-D 107 %, rubigan 95
%, propiconazole 86 %, triadimefon 71%, and metalaxyl 76 %. The recoveries
greater than 100 % represent both analytical error and matrix enhancement of the
residues. An acceptable analytical recovery would be 70 to 120 % (Leavitt, 1989).
Storage recovery studies were done for each pesticides by storing spiked solutions
for 6 months under the same conditions as the water samples. Storage recoveries

assess the potential for losses occuning during storage (EPA, 1992). The results

28

are isazophos 95 %, chlorothalonil 68 %, dicamba 114 %, 2,4-D 92 %, fenarimol

120 %, propiconazole 93 %, triadimefon 120%, and metalaxyl 70 %.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table 6 Pesticide Application Schedule to the Lysimeters for 1991 & 1992
Lysimeter 1 & 2 were constructed in 1990 & lysirneter 3 & 4 in
Application D1311. Pesticide kg ai/A Lysimeter
8/21/91 isazophos 1.02 1 & 2
3/21/91 chlorothalonil 4.34 ’ 1 & 2
9/ 17/91 dicamba 0.05 l & 2
9/ 17/91 2,4-D 0.52 1 & 2
5/3/92 rubigan 0.35 1 & 2
6/18/92 propiconazole 0.38 l & 2
7/21/92 triadimefon 0.69 l & 2
7/21/92 metalaxyl 0.69 l & 2
7/21/92 chlorothalonil 4.34 3 & 4
8/5/92 metalaxyl 0.69 3 & 4
8/5/92 chlorothalonil 4.34 l & 2
8/ 13/92 metalaxyl 0.69 3 & 4
8/20/92 chlorothalonil 4.34 3 & 4
9/4/92 chlorothalonil 4.34 3 & 4
9/4/92 metalaxyl 0.69 3 & 4

 

 

 

 

 

 

29

PART II - EFFECT OF COMPOSTIN G ON RESIDUES

This study was designed to determine the fate of triclopyr and 2,4-D
(Turflon II Amine), chlorpyrifos (Dursban), triclopyr and clopyralid (Confront),
isoxaben (Gallery), and flurprinridol (Cutless) in composted grass. June 12, 1991
the pesticides were applied to 0.23 acres of a mixed stand of Kentucky bluegrass
(Poa pratensis L.), perennial ryegrass (Lolium perenne), and fine fescue (F estuca
sp.). These were old stands of truf and varietal identification was not known. The
pesticides were applied at 0.64 kg ai/A chlorpyrifos (Dursban 4E), 1.2 kg ai/A
triclopyr plus 2,4-D (Turflon II amine), 0.91 kg ai/A triclopyr plus clopyralid
(Confront), 0.34 kg ai/A isoxaben (Gallery 75 DF) and 0.34 kg ai/A flurprimidol
(Cutless). Water was applied to plots that had isoxaben applied to move the
chemical into the grass and thatch layer, to avoid volatilization or
photodegradation. On June 13, 1991 the grass was clipped with a rotary mower
set at 3.8 cm. The inner 0.17 acres were collected for the compost piles. The
clippings were collected and brought to the Hancock Turfgrass Research Center
(Michigan State University, E. Lansing, M1) to establish the compost piles. Each
pesticide had two separate piles, one was left unturned for the duration of the
study and another that was turned weekly for the first 8 weeks of the study. A
control piles without any pesticide applied were made for use in background
studies. Samples were collected at l, 14, 28, 56, 128, and 365 days after

treatment (DAT). The interior and exterior of each pile was sampled and placed in

30

a one quart mason jar and transported to the laboratory (Pesticide Research Center,
Michigan State University, E. Lansing, M1), were they were stored at -10° C until
extraction. The interior of the pile was 15 cm from the surface of the compost
pile. This distinction became less apparent as the volume of the pile was reduced
and essentially not distinct after about 6 months. Method validation recovery
studies were conducted on each chemical and taken through the entire analytical
method in triplicate. The results were triclopyr, 72.0 %; isoxaben, 66.4 %;
flurprimidol, 143.5 %; clopyralid, 132.0 %; chlorpyrifos, 83.1 % ; and 2,4-D,
107.4 %. The nature of the sample from one sample to another and within a
sample period was variable. The samples could be dry, wet, contain fungal
growths, and various other debris with this great difference between samples, the
analysis was unique with each sample. To account for some on the variation dry
weight was reported for each sample. A 10 g sample was dried in a 104 ° C oven
over night and put in a dessicator and weighed after cooling. Pertinent physio-

chemical properties of each chemical are given in Table 7.

31

Table 7 Physio-Chemical Properties of the Test Chemicals

 

2,4-D < 7.5 x10'8 715 ' 2.7 60

Flurprirrridol 1.53 x 10'7 130 2.96

Tricolpyr 1.26 x 10*5 440 -0.69

Clopyralid 1.2 x 10" 1000

Isoxaben 3.9 x 10'7 1-2 2.64

Chlorpyrifos 1.87 x 10'5 2 4.70 6070
Dicamba 3.40 x 10" 4500 2.46 0
Metalaxyl 2.20 x 10*5 7100 16
Chlorothalonil 2.00 x 10‘ 0.6 2.88
Propiconazole 4.20 x 10'7 110 ~100
Triademefon 1.5 x 10'7 70 3.18 300
Fenar‘imol 2.20 x 10'7 13.7 3.40 2000
Isazofos 1.30 x 10‘4 250 3.80 100

1torr=1mmHg=75 bar=.075mbar

32

ANALYTICAL METHODS
STANDARD PURITY

All standards were purchased from Chem Service or directly from the
manufacturer. The purity of the standards is given in Table 8. Standards were
prepared from the dry powder and diluted with a solvent appropriate for the
solubility of the chemical and compatible with the GC analysis. The chemical
structure of all pesticides used in the two studies are given in Figure 4 and 5.

TABLE 8 Standard Purity
STANDARD PURITY

2,4-D 98.0
2,4-D Methyl ester 99
Triadimefon 97.6
Chlorothalonil 99.8
Chlorpyrifos 99.7
Clopyralid > 95
Dicamba 99.0
Flurprimidol 99.8
Isazophos 98
Isoxaben 92.5
Metalaxyl 99
F enarirnol 99.70
Propiconazole 97
Triclopyr 99.7

PART 1 - POTENTIAL FOR LEACHIN G
All samples were analyzed with High Performance Liquid Chromatography
(HPLC), antibody assay kits, or Gas Chromatography (GC) to determine the

amount of pesticide in the sample. Quantitation was performed by running a

Figure 4 Pesticide Structures

 

S -O‘—C H

NVN
Fenarirnol
/C\ -— CH2 N N—____'_
C3 H7
Propiconazole

CH3

CH3
1
. N/CH—T coocrr3
\co—CH OCH
. 2 3
CH3

Metalaxyl

33

\ Cl
Cl N/ coorr
Clopyralid
(cl \ Cl
0
/
/ CH c/
Cl N O_ 2 \OH
Triclopyr
OCHZCOZH
C1
C1
2,4-D
CH3\O
(I) CZHS
1
CH
C d
\T </ H l 3
C H
H o—-—-N 2 5
/0
CH3
Isoxaben

Figure 5 Pesticide Structures

COOH
Cl OCH3
Cl
Dicamba
{K
C
CH / \ 3
3 H3
Fluriprimidol

Chlorothalonil

 

34

f3H7
N
/ \
M ii 5
ll 0C2 H5
N———c ——-OP<::2
OCZHS
Isazofos
O
H
Cl OCHCC(CH 3)3
{:31 \
Triadimefon

35

standard curve for the pesticide in question to determine linearity of the range
being quantified. The sample was concentrated or diluted to bring it into the linear
range of the instnunent for the pesticide of concern. A single point calibration
standard was used to quantify the amount of pesticide in the sample. The calibra-
tion standard used to quantify the sample was one used to obtain the linear range
of the standard curve.

To determine chlorothalonil (Tetrachloroisophthalonitrile) in water a 100 g
sample (PAM-F DA, 1970) was placed in a 250 ml separatory frmnel with 20 g of
NaCl to increase the polarity of the aqueous solution. The water was extracted
with 20 ml of hexane three times and the hexane portions were combined and
reduced to about 1 ml for ECD-GC analysis.

Fenarirnol (El-Hadidi, 1993) (3 -(2-chlorophenyl)-3 -(4-chlorophenyl)-5-
pyrimidinemethanol) was determined by extraction of 100 g of water with 50 ml of
10% w/w NaCl solution and extracted twice with 40 ml of methylene chloride.
The methylene chloride portions were taken to dryness with a Turbo-Vap at 40-45
°C. An alumina column was prepared with a solvent extracted glass wool pledget
with about 13 g of alumina and 1.7 cm of Na2804. The column was rinsed with 10
ml of methylene chloride. The methylene chloride rinse is followed with 40 ml of
9:1 v/v methylene chloride:ethyl acetate solution and this was discarded. The
fenarimol was eluted with 99:1 v/v methylene chloride: methanol v/v solvent

mixture. The eluant was taken to dryness and brought to volume with hexane for

36

ECD-GC analysis.

Dicamba (2-Methoxy-3,6-dichlorobenzoic acid) (PAM-F DA, 1970) was
determined by acidifying a 100 g sample to pH 1 with 10 % H2804. The acidic
solution was extracted with 50 ml of diethyl ether 3 times and the ether extracts
are combined and reduced to about 10 ml. A Celite column was prepared with
100 g of Celite and washed with 40 ml of equal volumes of 2 M NaHzPO4 and 2
M K2 HPO4. Equilibrate 1.5 l of diethyl ether with 100 ml of the phosphate buffer
and remove the aqueous portion alter layers have separated. Add 15 g of the
washed Celite to a 1 cm i.d. column with equilibrated ether to keep packing
covered. The extract was added to the column and eluted with 265 ml of phos-
phate buffered ether. The volume of eluant was reduced to about 2 ml for
deriviatization with diazomethane. The volume was reduced and brought to
volume for ECD-GC analysis.

Triadimefon (l-(4-Chlorophenoxy)-3,3-dimethyl-l-(lH-l,2,4-triazol-l-yl)—
2-(butanone) was extracted from 100 g water with 50 ml of chloroform 3 times
and the extracts are combined. The extracts are taken to dryness and a F lorisil
column was prepared with a glass wool pledget placed in the bottom, 10 g of 2.5
% deactivated Florisil and topped with 5 g of anhydrous Nast4 to a 20 mm i.d.
column. The column was rinsed with 6:4 v/v hexane:ethyl acetate mixture. The
residue was dissolve in 10 ml of the hexane:ethyl acetate mixture and transferred

to the column. A flow rate of 2-3 draps per second was maintained of 150 ml of

37

hexanezethyl acetate and all eluant was collected. Take the extract volume to
dryness to remove the hexanezethyl acetate and bring up in hexane for compatibil-
ity with the GC for analysis.

Isazofos (0-(5-chloro-l-{methylethyl}-1H 1,2,4-triazol-3-yl)0,0—diethyl
phosphorothioate) was extracted with 20 ml of chloroform 3 times. The NaCl was
added to the water to increase the polarity so as to favor partitioning isazofos into
the organic phase. The chloroform extracts were combined and reduced to about 1
ml in the Turbo-Vap. Analysis of isazofos was with the nitrogen/phosphorus
sensitive detector equipped with a DB-S capillary column.

Millipore Corporation's immunoassay test kits were used to determine 2,4-
D in water samples obtained from the lysirneters. The samples detected on the
basis of polyclonal antibodies which compete for 2,4-D residues (in the sample)
and 2,4-D enzyme conjugate (in the kits). The 2,4-D in the sample competes with
the 2,4-D enzyme conjugate for a limited number of antibody binding sites.
Solutions of substrate and chromogen were added to the test tubes. The 2,4-D
enzyme conjugate causes the chromogen to turn blue. The quantity of 2,4-D was
determined by the intensity of the color. The greater the amount of 2,4-D the
lesser color development because of the competition with the enzyme conjugate.
The amount was quantified by visible spectroscopy at 450 nm.

Metalaxyl (N -(2,6-Dimethylphenyl)-N-(meth6xyacetyl)-alanine methyl

ester) was extracted from 100 ml of water with two 25 ml portions of toluene and

38

put through 0.5 g of anhydrous Na2SO4 to remove the aqueous residue. The
toluene extract was reduced to dryness and brought up to 4 ml with methanol and
was ready for HPLC analysis. The HPLC column was a Speri-S RP-18, 5 micron
which was 220 X 4.6 mm i.d. A 50:50 v/v acetonitrile and water was applied with
a flow rate of 1.5 ml / min. A 50 ul injection loop was used for sample injection.
A UV detector at 220 nm is used to detect Metalaxyl.

Propiconazole( l-{2-(2,4-dichlor0phenyl)4-propyl-1,3-dioxolan-2-ylm-
ethyl]-lH-l,2,4-triazole) was extracted from water by adding 20 g NaCl to move
the organic compounds out of the water and into dichloromethane. Three 20 ml
portions of dichloromethane were used to extract propiconazole from the aqueous
phase. The three portions of dichloromethane were combined and reduced to 1 ml
by adding lml of isooctane as a keeper solvent. The extract was now ready for

GC injection. A N/P flame ionization detector was used for detection.

39

PART II - EFFECT OF COMPOSTINGS ON RESIDUES

All samples were analyzed with High Performance Liquid Chromatography
(HPLC) or Gas Chromatography (GC) to determine the amount of pesticide in the
sample. Quantitation was performed by running a standard curve for the pesticide
in question to determine linearity of the range being quantified. A single point
calibration standard was use to quantify the amount of pesticide in the sample.

Determination of chlorpyrifos (0,0-Diethyl-O-[3,5,6—trichloro-2-pyridyl]-
phosphorothioate) in grass was with an Electron Capture Detector (ECD) GC.
Approximately 10 g of grass was extracted for each analysis. The grass was
homogenized with 100 ml of acetone for 5 to 10 minutes and then filtered with 0.5
cm of HyFlo Super Cel (J ohns-Manville) in 150 ml sintered glass funnel on a
vacuum filtering assembly. The Hyflo Super Cel (diamtomaceous earth) is an
extremely weak adsorbent and was used for very polar contaminants (Heftmann
1967). The extraction was repeated with a fresh 100 ml of acetone. The filtrates
are combined and taken to dryness.

The extract was transferred with 20 ml of hexane to a prewashed column
for cleanup. The extract was placed in a column with 1.5 g of 60 to 100 mesh
silica gel (oven dried at 110° C for 4 hours) with a glass wool (solvent extracted)
pledget in the bottom of a 1 cm internal diameter glass column. Silica gel has a
slightly acidic adsorbent character. The surface hydroxyls attached to silicon

atoms are responsible for the adsorptive properties which are adsorption of polar

40

or unsaturated molecules (Heftrnann 1967). Three 20 ml portions of hexane was
used to elute the sample through the column. The combined eluted hexane was
taken to dryness with a Turbo-Vap and brought to volume with acetone for the GC
injection.

Gas chromatography was performed by Perkin-Elmer 8500 instrument
equipped with Ni63 ECD. The oven temperature was held at 200° C, the injector
temperature was 250° C, and the detector was 345° C. The canier gas (helium)
flow rate was 15 psig and the makeup gas is N2. A DB-S capillary column 0.25-
um film thickness 30m long with and internal diameter of 0.32 mm. The
chlorpyrifos standards were obtained fi'om Chem Service, Inc. with a purity of
greater than 99 %.

Determination of clopyralid (3,6-Dichloro-2-pyridinecarboxylic acid)
(Galoux, 1982) in grass was done with a ECD GC. About 10 g of grass was
homogenized for 5 minutes with 150 ml of 0.25 M KOH. The extract was trans-
ferred to a 500 ml separatory funnel via a Whatrnan # 1 filter. One hundred ml of
diethyl ether, 5 g of NaCl and 20 ml of H2SO4 were added to the separatory funnel.
The diethyl ether layer was collected and the extraction was repeated with fresh
diethyl ether. The combined extracts were put through a anhydrous NaQSO4 bed to
remove any water and the volume was reduced to about 1 ml.

The clopyralid extract was then esterified with diazomethane, the volume

was reduced to < 0.5 ml and then brought to volume for GC analysis. The

41

clopyralid samples were run with the same GC conditions as the chlorpyrifos
samples. The clopyralid standards were obtained from Chem Service, Inc.

Determination of triclopyr (3,5,6-Trichloro-2-pyridinooxyacetic acid) in
grass was done with a ECD GC. The 10 g sample was shaken for 10 minutes with
6 g of NaCl, 1 ml of 9 M H2S04, 50 ml of diethyl ether and 50 to 100 ml of H20.
The extract was filtered through a Whatrnan # 1 with a vacuum applied. The
filtrate was then transferred to a separatory funnel and the ether portion was
retained. The aqueous portion and filter paper was then shaken with 50 ml of
diethyl ether for 10 minutes. The ether portion was separated and combined with
the other ether portion. The extract was washed twice with 20 ml of 10 % NaCl
w/v, and dried over anhydrous NaQSO4. The volume was then reduced to almost
dryness. .

A silica gel colrunn was prepared by adding 3 g of silica gel to a 1 cm
internal diameter glass column in a hexane slurry. The column was washed with
100 ml of toluene and hexane (10 % : 90 %) v/v. The extract was added and then
eluted with 100 ml toluene and hexane (35 % : 65 %) v/v. The volume was reduce
to < 0.5 ml and esterified with BF3 in methanol. The extract was held at 80 °C for
1 hour. The sample was then transferred with hexane to a separatory funnel,
washed twice with 20 ml of 10 % NaCl w/v, and dried over anhydrous NaZSO4.
The sample was reduced in volume for the GC. The GC used was the same as was

used for the chlorpyrifos samples.

42

F lurprirnidol (alpha-(1-methylethyl)-alpha-[4-(trifluromethoxy)phenyl]-5-
pyrimidinemethanol) in grass was done on the ECD GC using solid phase
extraction with an basic alumina column (Alltech 500 mg). The basic alumina has
a hydrophilic polar surface character capable of adsorbing the hydrophilic species
from the nonaqueous solutions. The grass was refluxed for 1 hour in 4:1
methanolzwater v/v in a boiling flask with water cooled reflux condensing tube.
After cooling, the extract was filtered through a Whatrnan # 7 filter into a
separatory frmnel with 30 ml of 5 % NaCl w/v. The flurprimidol solution is
extracted three times with 50 ml of hexane and the hexane extract was then passed
through anhydrous Na2S04. The hexane extract was then evaporated to dryness
and brought to 3 ml with dichloromethane and put on to the Alumina Sep—Pak
cartridge. The flurprirrridol was eluted off of the Sep-Pak with 3:1
dichloromethanezmethanol v/v solution. The Perkin-Elmer GC with the same
conditions is used for the flurprirrridol as was used for the Chlorpyrifos samples.

Determination of isoxben (N -[3-(l-Ethyl- l-methylpropyl)—5-isoxazolyl]-
2,6-dimethoxybenzamide) in grass was done with HPLC. The grass was ground
and extracted with 150 ml of methanol by shaking for one hour on a gyratory
shaker. The sample was then filtered through a Whatrnan # 1 filter paper in a
Buchner funnel with the aid of vacuum. The plant material and filter paper were
returned to a pint jar and shook for half an hour with 100 ml of methanol. Again

the extract was filtered as above in a Buchner firnnel and the filtered extracts were

43

combined and transferred to a 1000-ml separatory frmnel. Seventy-five milliliters
of a 5 % NaCl solution and 200 ml of water were added to the separatory funnel.
The solution was extracted with two 125 ml portions of n-Hexane and the n-
Hexane was discarded. This was followed with three 70 ml extractions with
dichloromethane. The dichloromethane was passed through anhydrous sodium
sulfate bed to remove the water. The dichloromethane extract was evaporated to
dryness and transfer through a alumina/florisil column with dichloromethane.
The column was washed with 50 ml of 4:1 dichloromethane/ethyl acetate v/v and
25 ml of 99: lv/v dichloromethane/methanol and the eluate was discarded. Fifty
ml of 99:1v/v dichloromethane/methanol was put on the column and the eluate
was collected. The solvent volumes used in the alumina/florisil column should be
verified with each new batch of alumina and florisil. Evaporate the eluate to
dryness and add 2 ml of 2 % KMnO4 w/v and swirl. Then add 2 ml of 2 M KOH,
followed by 4 ml of dichloromethane and shake vigorously. Let the solution stand
for 5 minutes and remove the dichloromethane layer and dry though anhydrous
sodium sulfate. Repeat the addition of dichloromethane step twice and combine
dichloromethane washes. Evaporate the dichloromethane to dryness and bring to
volume for HPLC analysis in the mobile phase of 60:40 methanol/water.
Determination of 2,4-D (2,4 dichlorophenoxy acetic acid) was done by
extraction of 10 g of grass with 5 ml of H20, 8 ml of HZSO4, and 50 ml of

methanol by shaking for 20 minutes. The extract was filtered through a Whatrnan

44

#1 Filter. The process was repeated with fresh solvents on the filter paper. The
combined filtrates are reduced to the H20. The aqueous extracts are extracted
with two portions of 50 ml of methylene chloride and reduced to about 1 ml with
N2. A 1 cm i.d. Florisil column was prepared with 3 g of Florisil and about 2-4
mm of NaZSO4 and 30 ml of petroleum ether was rinsed through and discarded.
The sample extract was placed on the column, followed by 15 ml of petroleum
ether and the eluate was discarded. Elution of 2,4-D was accomplished by adding
25 ml of 1:1 v/v petroleum ether and ethyl ether. The eluant was reduced to less
than 0.5 ml.

The acidic group on 2,4-D was esterified to a methyl ester by reaction with
diazomethane. The extract was reduced to less than 0.5 ml and brought up to

volume for ECD-GC analysis.

45

RESULTS AND CONCLUSIONS
PART I - POTENTIAL FOR LEACHIN G

The pesticides generally did not make it through the lysirneters to the
collection point or were not of sufficient concentration to be detected. Each
pesticide has a finite capacity for sorption to the soil in the lysirneter due to the
finite amount of soil available. The concentration of the residues from the
leachatc analysis are given in Appendix B. The rate of accumulation in the soil is
influenced by the rate of the pesticide addition to the soil and the rate it is moved
out of the soil. The rate of addition is dependent on the sources and application
schedule, while the rate of disappearance is related to the concentration,
volatilization, degradation, photolysis, runoff, and leaching, all of which occurs
continuously.

Immediately after spraying, the chemical will partition between air, water,
soil, and biota. The tendency of a persistent chemical to partition to a specific
phase in the environment, determines were in the environment it will be found and
the relative concentration in these environmental phases. If any of the phases has
a sink or essentially infinite capacity as compared to the other phase then the
chemical will go to infinite dilution and detection will not be achieved in the
lysirneter. Of course if the chemical is hydrophilic it will stay within the water
and if of sufficient concentration will be detected during analysis. Kow is a good

indicator of hydrophobicity and would predict the favored partition phase a

46

chemical would be found. Soil sorption is often shown to have a correlation to
K0“, the partitioning of a solute between two immiscible solvents, water and
octanol (Chiou and Schmedding, 1982 and 1983). This relationship would imply
if a compound has a high Kow then a high sorption to soil, especially if the soil has
high organic content. K0w can be used to predict the potential for sorption to
nonpolar or polar compounds. If a chemical tends to favor sorption to OM and
the soil is of high OM then the chemical will not be seen in the lysirneter drainage
in sufficient quantity to be above instrumental detection levels. Volatilization,
chemical degradation, runoff, and sorption both in soil and thatch remove the
intact pesticide from moving down through the lysirneter. Degradation by
rrricrobes is affected by the amount of moisture and sorption of the pesticide to the
soil or thatch. In a study conducted at Kentucky State University (KSU) it was
shown that landscape features such as living turf mulch between crop rows
prevents surface water pollution from pesticides but increases infiltration of
pesticides into the soil profile (Byers, 1995). The treated turf in the KSUstudy
though it did have greater infiltration depths , down to 1.5 m, within 3 months it
was only at trace concentrations, which was similar to the conventional tillage.
Transport of pesticides by runoff is a function of rainfall, hydration of the soil,
and vegetative characteristics. If there is a lag between application and rainfall,
the probability of runoff is decreased due to plant uptake, degradation, and

volatilization. Each chemical will volatilize at a difl‘erent rate due to its vapor

47

pressure, sorption to soil or plants, hydration of the soil, temperature, and pesticide
concentration. Ifthe water solubility of a chemical is sufficiently high as to
facilitate transport with water as it moves up and down the soil horizon in response
to moisture levels, it will not be seen in the lysirneter drainage until the lysirneter
has been sufficiently hydrated to drain past the vadose layer of soil.

The soil column will be composed of solid soil particles, water, air, and
organic oils from breakdown of organisms and plants. The pesticide will partition
between the different phases of hydrogeological environment according to its
chemical properties. The lateral movement in the lysirneter is reduced due to the
sides of the lysirneter so disregarding this movement or assuming it to be
negligible will be appropriate for this discussion. The potentially highest
concentration of a chemical to go through the lysirneter was chlorothalonil at 1.4
mg/ml (1400 ppm) and the lowest dicamba 0.3 ppm. This concentration assumes
the mass to move at constant velocity through the soil profile but this will not
occur. The chemical may travel as a vapor or liquid dissolved in the water or as a
oil at the junction of the water. The pathway of transport will have different
porosity and constituents to retard the velocity which will cause the chemicals to
dilute along the path.

Chlorothalonil was not detected in the lysirneter drainage and that can be
supported by its insolubility in water (0.6 mg/l) and high affinity for silty and Clay

loam soils. The half-life in aerobic soils is from one to three months but combined

48

with its hydrophobic character it is unlikely to find its way to groundwater. In
laboratory studies Chlorothalonil has been shown to hydrolyze to 2,3,5-trichloro-
4-hydroxyisophthalonitrile, with half-lives as short as four hours (Lawruk, 1995).

Dicamba was not detected in the lysirneter over the course of the study.
Dicamba is highly water soluble (500,000 mg/l) and with this it would seem likely
to make into the water before break down. Leaching from the soil should occur in
3-12 weeks but the typical half-life is one to four weeks so if the chemical does
not immediately move to the water phase then degradation may further reduce
concentrations in the soil and thatch layer.

Metalaxyl has a one to eight week half-life in soil under typical field
conditions and degradation may be accelerated by photodegradation to about 2
weeks. Metalaxyl was not detected in the lysimeter and degradation and binding
to plant material may account for this.

Triadimefon was detected twice in one lysirneter and three times in another,
at essentially the same time in each lysirneter. The first detection was 56 days
after application of triadimefon to the site in lysirneter 2, 86 days in lysirneter l,
131 days again in both lysirneters, and a final detection at 146 days in lysirneter 2.
The compound is very stable in water at pH 3.0, 6.0, and 9.0 up to 28 weeks. If
the chemical moved into the water soon after application this may account for the
detection on the various days because the soil half-life is about eighteen days. The

rainfall and irrigation data for the period from 1 day before to 9 days after

49

triadimefon application showed 8.01 cm of precipitation. The large amount of
precipitation could facilitate the travel through the turf and thatch layer, directly to
the water in the soil profile.

All the remaining compounds were not detected and this would be due to an
array of causes. A similar study was conducted at the University of Georgia
College of Agriculture Experimental Station (unpublished data conducted by A. E.
Smith and D. C. Bridges) with lysirneters 20 % (about 2.2 X 10" m3)of the size
used in the studies conducted at MSU. Dicamba was applied. at 0.07 kg/ha and
2,4-D at 0.28 kg/ha and the leachatc was having positive detection of 2,4-D at 21
days and dicamba at 7 days after treatment. The leachatc was collected for 70
days and positive detection occurred throughout that time. The lysirneters were
constructed with 10 cm gravel, 7.5 cm coarse sand, and 35 cm of sterilized rooting
mix. The sand and gravel are natural leachers which contrasts to the lysirneters
used at MSU, being of undisturbed sandy loam soil. The sterilization eliminates
microbes for degradation of the pesticides. Even with this system that favors
leaching over the MSU lysirneters less than 1.0 % of the applied pesticides were
recovered in the lysirneter leachate.

Although the intact pesticides were not detected in the leachatc, it supports
the idea of degradation, sorption to thatch or turf, or moving away from the
lysirneter by volatilization or photodegradation on the surface to be occurring. If

the pesticide remains in the turfgrass system, then assessing the use of composting

50

to degrade pesticide as a means of decreasing residue levels would be appropriate.

51

PART II - EFFECT OF COMPOSTING ON RESIDUES

Patterns of chemical loss in the compost piles was similar in all of the
pesticide treatments. Isoxaben (Figure 10 and 11), flurprimidol (Figure 12 and
13), triclopyr (Figure 8 and 9), and chlorpyrifos (Figure 6 and 7) all were below
the detection limit of the methods used after 365 days. Clopyralid (Figure 16 and
17) and 2,4-D (Figure 14 and 15) were reduced to 1.4 ppm and 1.3 ppm
respectively after 365 days. The chemicals tend to show a biphasic degradation.
There was generally an initial rapid dissipation rate followed by a slower process.
The first phase of chemical loss may be related to volatilization and photolysis
while the second phase chemical loss by rrricrobial degradation. The reasoning
being that the microbial population was not there or other energy sources were
available at the earlier times for the microbes to consume. Table 9 shows the first-
order decay constants, k (day'1) (Frederick, 1994), for each pesticide at various
times. The values are calculated between the first detection (initial concentration
or A) and the next interval with a detected concentration (X) sample interval. The
initial recovery for each chemical is A, where X equals the concentration at time t.

These values were determined by the equation:

X = Ae “k"

The variation in the k value would not lend itself as a good parameter to predict

chemical loss from the compost pile. If the k value was used for the entire study

52

you would predict all chemicals to leave the pile either by loss to environment or
metabolic changes.

The sampling in the field had inherent difficulties. The compost piles were
not homogeneous masses. Within the piles there could be aggregate population of
degrading organisms and this produced unequal rates of decline of the chemicals
within the piles. The sampling suffered from aggregate distribution of chemical
and microbes and may account for a portion of the variation seen in the results. If
the sampling occurred in an area were the population of degrading organisms was
high, then the chemical may be absent or at a low‘concentration and conversely if
sampling took place at an area of low population of degrading organisms then the
chemical concentration may be high.

The pesticide concentrations of each chemical in each is given in Appendix
A (pp 60- 62 ) and the graph that accompany the text are normalized to the highest
value, with the highest normalized value being one. This allows for comparison
between chemicals of the relative changes without comparing absolute
concentrations, ie. allows evaluation of the timing of the changes. All of the
values given for the pesticide concentrations are given in dry grass weight. The
reason for choosing dry weight was that the variation in the composition of the
samples appeared to be great. The determination of percent water confirmed the
variation in physical appearance. The percent water ranged from < 1 % to greater

than 70 %.

53

mnHm mzk monzH
unflpmoasoo oOCHw m>mo

own mma om . mm 42

 

 

 

 

 

 

nmcczpcanu
Umcczknn

 

 

 

 

Figure 6 Chlorpyrifos Inside the Pile

 

r ,-
\\\\\\A _. T—
l LILLJ l J l IJ\J l l I J 1L1 ij 1

(\l
1'—

 

 

 

 

AnmNHHmscozv COHHmchmocoo

QmNH4<2moz

mo... Hm>nEOIEO

 

N.o
To.
0.0
m6

F

54

Figure 7 Chlorpyrifos Outside the Pile

 

 

UmCLzhua

 

 

 

mnHm mxh monpao
mafipwoqsoo macaw m>mo

0mm wNF mm mm .vw
_

_ _ —

_

- a .
n x
o

 

 

 

 

 

 

 

1....IE..\II..III.

 

 

 

 

 

 

 

AnmNHHmELozv coapmeycmocoo

QmNngzmoz

mo... H m>n_ H $0410

 

N.o
¢.o
0.0
m.o

55

Figure 8 Triclopyr Inside the Pile

mmHm mTE. monzH

mafiymoasoo mosaw w>mo
mmm mm? mm mm VF

_ _ _

F

_

 

 

 

nmcczpcal
noses».-
umcczwcaun
accuse-

l

 

 

\

 

 

 

 

\
11411

 

 

 

l l l

 

r l

\

 

 

 

 

AumNHHmELozv coapmcecmocoo

.omNHn<2moz

EEODOHE.

 

mnHm m1» monhao
mafiuwoaeoo occaw.m>ma

mmm mm? mm mm 42

.LIInnru--Irax--lxr--T‘x

N.0

 

56

 

     

v.0

 

umccsucnun
Umccshuu
umcczwcauu
nmcczkun

0.0

 

.' , f up.”

3 .I‘ 1‘31, - \_A"‘j:;"5i"1»; . \’;;:’, 31?}. ’1:

5-e. '1 i,:-‘. CW""¥"\W3'.
\\\ _ 1—
\Jlrlllrrllrr llJ

-

 

\

 

\

 

Figure 9 Triclopyr Outside the Pile

 

  

 

\
\
I .\l
‘—

 

 

 

 

 

AuoNHHmELon cOHmeycmocoo

0mNH4<§m02

m>1040HmH

57

Figure 10 Isoxaben Inside the Pile

013m 010. monzH

 

 

 

 

 

853:0.
umcczhnn

 

asapwoasoo mOCHm m>mo
v? F
_ _ I
wan .\

 

 

\\

 

 

’\

 

\

'\

 

 

 

 

AUmNHHmELozv coaymepcmocoo

omNH4<§m02

. zmm<x00H

1111'!

l

\
‘1 r r\~l l x

l l

 

58

Figure 11 Isoxaben Outside the Pile

mem mIH monhao

mafipmoaeoo mocflw m>mo
0mm mm? mm mm er

_ _ _

 

 

 

 

853:3.
nmcczhnu

 

 

 

l

 

 

 

 

 

 

 

 

 

\\\\\ _‘_
..\I.I.I...II...I”.1...

N
1'-

 

 

 

 

 

AumNHHmELozv coapmeycmocoo

QMNHIESEOZ

zmm<xomH

N.0
v.0
0.0
0.0

P

59

Figure 12 Flurprimidol Inside the Pile

mDHm mIH monzH
mcflpmoqsoo macaw w>mo

 
  

 

   
 

0mm. mNF mm mm. v._. _. O

N.O

. So

nmccsycsnn mam. ........... . ............. «m. m . - , m 0.0

_ umcezhnu ............... m.o
F

..................... N._.

 

   

AuoNflHmELozv EOAHmecmocoo

0mN3<2m02

1_00H_>_Hmn_m01_u_

60

Figure 13 Flurprimidol Outside the Pile

 

 

 

 

 

nmccaycanu
nmcczH-n

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

nooHEHmamann.

mafipmoasoo mOCHw w>mo
omm mmw mm mm v? F

_ _ _ . _ _ _ -
Ll-l-‘V . Ma .. . H
l x.”
.\ r
..\.M
.\,

AnmNHHmELon scepmcycmocoo

0 mN H ._<2m02

 

mmHm 01H mQHmHDO

N.0
¢.0
0.0
0.0

Figure 14 2,4-D Inside the Pile

2,.4-D

NORMALIZED

Concentration (Normalized)

 

 

 

IlTurned
IIUnturned

 

 

 

 

 

 

 

 

 

 

: .'I _ (I ') ’.‘ r .\ .;‘ '1'
-\. I -—-r
\\ p ,
\
r \\l L r r \l r r r r 1 r l r L\l r .L

LCD-V N O

(\1

F

128

Days Since Composting

 

F

(I)
0000

356

 

INSIDE THE FILE

mnHa DIP moneao
QCHumoqsoo macaw w>mo

 

 

 

 

 

 

62

 

 

 

 

 

Figure 15 2,4-D Outside the Pile

 

 

0mm 0WF flm mm vw w 0
..‘ m N. o
w..111111 - A
umccsucsnn \\wvm0.o
accuse-I \\A\mm.o
.\\.E 2
\\ N . r

 

 

 

 

AUmNfiHmscozv COHymLycwocoo

QMNHIESmoz

aim

63

Figure 16 Clopyralid Inside the Pile

qum mI._. monzH

mcflymoasoo macaw m>mo

 

 

 

 

 

nmccswcnnu
nocczh-u

 

 

 

 

 

 

 

 

 

 

N.
L L lAi‘i‘J l I .l.\‘J J. L

 

 

 

 

AumNHHmELozv COHymecmocoo

QmNHD/Emoz

QHS<¢>aono

 

N0
#0
0.0

64

Figure 17 Clapyralid Outside the Pile

C LOPYRALI D

NORMALIZED

Concentration (Normalized)

 

llTurned
IlUnturned

 

 

 

 

 

 

 

 

\

\

\.

(v

F

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

., way-1...; «“259 m, ‘5 b fiNr/m 33.536138?“ '
i ‘ m“

\g

\ \
IIJII\I\JIII\JJI\III JJII

T-(DQYNO
OOOO

 

28 56 128 356

14

Days Since Composting

OUTSIDE THE FILE

65

Table 9 First-order decay constants of the disappearance of applied Pesticides

 

We SthCV CV
Chlorpyrifos 3-A-IN* 0.050

3-B-IN 0.224

3-A-OUT** 0. 100

3-B-OUT 0.263 0.159 0.10 0.63
Triclopyr 3-A-IN #

3-B-IN 0.226

3-A-OUT -0.234

3-B-OUT 0.024

4-A-IN -0.095

4-B-IN 0.033

4-A-OUT 0.024

4-B-OUT -0.248 -0.039 0.17 4.36
2,4-D 3-A-IN -0.067

3-B-IN 0.209

3-A-OUT -0.038

3-B-OUT 0.106 0.053 0.13 2.45
Clopyralid 4-A-IN -0.055

4-B-IN 0.141

4-A-OUT 0. 18 1

4-B-OUT 0.099 0. 104 0.10 0.96
Isoxaben 5-A-IN -0.043

5-B-IN 0.143

5-A-OUT -0.069

5-B-OUT 0.698 0.183 0.36 1.97
Flurprirrridol 3-A-IN -0.022

3-B-IN 0.063

3-A-OUT -0.098

3-B-OUT -0.060 -0.030 0.070 2.33
Average of All 0.072 0.094 1.31

 

* IN is inside the compost pile, A is the pile is turned

** OUT is outside the compost pile, B the pile is not turned

66

The research on 2,4-D (Table A5, pp 72) has shown a decline from a high
of about 183 ppm to less than 2 ppm in 365 days. 2,4-D was applied to bluegrass
turf at 0.73 kg ai/acre in a laboratory experiment (Extoxnet, 1993) and a half-life
of ten days was determined. Other studies have shown half-lives of 1.5 to 16 days
in non-sterile soils. EPA has included 2,4-D in a list of chemicals likely to leach
from soil and this agrees with the water solubility of 890 mg/l but the persistence
as indicated in the half-lives implies that it will breakdown before becoming a
ground water problem. 2,4-D has been found in five states groundwater and
surface waters (Extoxnet, 1993).

Studies have shown chlorpyrifos (Table A1, pp 70 ) to be relatively
persistent as compared to 2,4-D in that the half-life can range from 2 weeks to over
a year, this research confurns the long half-life in that at 56 days chlorpyrifos was
still detectable at 0.7 ppm and 0.1 ppm at 128 days. Some of the persistence can
be related to it strongly absorbing to soil particles and grass.

All of the chemicals except 2,4-D and clopyralid (Table A6, pp72) were
below detection at 365 days, although 2,4-D had a high concentration of 183 ppm
at initiation it was down to 1.4 ppm after 365 days. Clopyralid declined from 32
ppm to less than 1.4 ppm after 365 days.

In summary for all the chemicals applied, the composting environment has
shown itself to be a good degrader of pesticides. The initial concentrations could

cause damage to plants if applied immediately after composting but within several

67

months the compost piles should be benign enough to apply to gardens.

Future studies should control the variability by taking more samples from
the piles and then compositing them as one sample, also increasing the number of
replicate piles. Future work could focus on the metabolites also. Further studying
of the depth of penetration of the pesticide within the turf and thatch layer would
bring some understanding as to were the pesticide goes after application.
CONCLUSIONS

The two studies complement each other in the aspect of showing that
degradation and control of pesticides after application is a multi-faceted task. The
lysirneter study showed that significant movement of pesticides to groundwater is
unlikely in typical applications to vegetative areas. Laboratory studies indicate
considerable pesticide mobility, leaching in field situations are effected by soil
adsorption , degradation, and upward movement of water in response to
evaporation. Movement of pesticides at high flow velocities show increased
penetration in the soil column (Leonard, 1976) and this was evident in the
detection of triademefon in two lysirneters by the large amount of rain recieved
before and after the application to the turf.

Pesticides applied to turfgrass may be found in the clippings for several
months after application. . Two, four-Dichlorophenoxyacetic acid and clopyralid
' were found in composted turf up to one year after application. The composting of

turf showed greatly reduced to non-detectable residues in the turf after one year.

68

Knowledge of the behavior of pesticides in the terrestrial environment is
paramount before release, to avoid past mistakes and future problems as seen in

organochlorine pesticides.

APPENDICES

APPENDIX A--TURF GRASS COMPOST DATA

69

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

APPENDIX A
TURFGRASS COMPOST DATA
TABLE A1 CHLORPYRIFOS CONCENTRATION (ppm)
DAYS SINCE PESTICIDE APPLIED

SAMPLE # l 14 28 56 128 356
3-A-IN 0.04 nd 0.01 nd 0.04 nd
3-B-IN 0.23 0.01 nd nd nd nd
2-A-OUT 0.82 nd 0.05 0.21 0.1 1 nd
2-B-OUT 6.8 0.17 nd 0.73 0.11 nd

TABLE A2 TRICLOPYR CONCENTRATION (ppm)

DAYS SINCE PESTICIDE APPLIED

SAMPLE # 28 56 128 356
3-A-IN nd nd 0.45 nd nd nd
3-B-IN 0.94 0.04 0.03 0.26 . 0.48 nd
3-A—OUT 0.12 3.18 0.02 0.17 nd nd
3-B-OUT 0.07 0.05 0.01 nd 0.17 nd
4-A-IN 0.05 0.19 0.07 0.05 nd nd ,
4-B-IN 0.30 0.19 0.04 0.14 0.07 nd
4-A-OUT 4.54 nd nd nd 0.21 nd
4-B-OUT 0.22 7.13 0.05 0.15 0.11 nd

 

 

 

 

 

 

 

 

 

 

70

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

TABLE A3 ISOXABEN CONCENTRATION (ppm) ’
DAYS SINCE PESTICIDE APPLIED
SAMPLE # 1 14 28 56 128 356
5-A-IN 8.12 14.72 0.59 2.22 0.98 11d
5-B-IN 36.83 4.99 13.68 1.90 3.20 -nd
5-A-OUT 4.98 12.99 5.09 10.58 10.17 nd
5-B-OUT 175.51 32.35 76.27 49.99 0.81 nd
TABLE A4 FLURPRIMIDOL CONCENTRATION (ppm)
’ DAYS SINCE PESTICIDE APPLIED
SAMPLE # 1 14 28 56 128 356
6-A-IN 2.24 nd 4.19 1.14 1.73 nd
6-B-IN nd 3.67 1.53 0.97 2.21 nd
6-A-OUT 0.43 1.69 0.55 1.00 2.52 11d
6-B-0UT 2.36 5.50 0.17 2.35 1.75 nd

 

 

 

 

 

 

 

 

 

 

71

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

TABLE A5 2,4—D CONCENTRATION (ppm) ‘
DAYS SINCE PESTICIDE APPLIED
SAMPLE # 1 14 28 56 128 356
3-A-IN 38.12 97.02 3.71 nd nd nd
3-B-IN 86.61 nd 0.25 nd nd nd
3-A-OUT 26.32 nd 75.79 nd 0.62 0.51
3-B-OUT 183.15 41.54 11.42 6.06 nd 1.37
TABLE A6 CLOPYRALID CONCENTRATION (ppm)
DAYS SINCE PESTICIDE APPLIED
SAL/IPLE # 1 14 28 56 128 356
4-A-IN 15.6 16.8 0.3 0.5 31.9 1.3
4-B-IN 7.2 1.0 46.9 0.3 9.6 0.6
4-A-OUT 32.0 nd 0.2 0.2 10.6 0.9
4-B-OUT 6.8 1.7 7.7 0.4 4.7 0.1

 

 

 

 

 

 

 

 

 

 

APPENDIX B--WATER.LYSIMETER DATA

Table BO Sample Dates for Water Collection

72

APPENDIX B

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sample # Date Sample # Date Sample # Date Sample # Date
1001 5/1/91 1024 2/27/92 1047 9/4/92 1070 4/5/93
1002 5/17/91 1025 3/7/92 1048 9/8/92 1071 4/13/93
1003 6/12/91 1026 3/18/92 1049 9/10/92 1072 4/21/93
1004 7/22/91 1027 3/25/92 1050 9/15/92 1073 4/22/93
1005 8/17/91 1028 3/27/92 1051 9/29/92 1074 5/11/93
1006 8/23/91 1029 4/4/92 1052 10/15/92 1075 6/8/93
1007 8/29/91 1030 4/10/92 1053 Missing 1076 6/9/93
1008 8/30/91 1031 4/16/92 1054 10/26/92 1077 6/24/93
1009 9/3/91 1032 4/21/92 1055 11/3/92 1078 7/9/93
1010 9/16/91 1033 4/24/92 1056 1 1/12/92 1079 7/27/93
1011 10/22/91 1034 4/25/92 1057 11/13/92 1080 7/30/93
1012 10/26/91 1035 4/27/92 1058 11/20/92 1081 8/5/93
1013 10/27/91 1036 5/6/92 1059 11/23/92 1082 8/17/93
1014 10/30/91 1037 6/8/92 1060 11/29/92 1083 8/24/93
1015 11/8/91 1038 6/17/92 1061 12/14/92 1084 9/14/93
1016 11/20/91 1039 7/792 1062 12/28/92 1085 9/21/93
1017 11/23/91 1040 7/14/92 1063 12/31/92 1086 9/28/93
1018 12/3/91 1041 7/16/92 1064 1/4/93 1087 10/7/93
1019 12/12/91 1042 7/20/92 1065 1/4/93 1088 10/19/93
1020 12/18/91 1043 7/29/92 1066 1/8/93 1089 10/22/93
1021 1/3/92 1044 7/31/92 1067 1/29/93 1090 11/16/93
1022 1/22/91 1045 8/4/92 1068 3/9/93 1091 12/9/93
1023 2/21/92 1046 Missing 1069 Missing 1092 12/23/93

 

 

73

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B1 Bayleton Residue Data
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(PPm) (PPm) (PPm) (Ppm)
1001 # 1024 # 1047 * 1070 *
1002 # 1025 # 1048 * 1071 *
1003 # 1026 # 1049 * 1072 *
1004 # 1027 # 1050 * 1073 *
1005 # 1028 # 1051 * 1074 *
1006 # 1029 # 1052 0.03 1075 *
1007 # 1030 # 1053 Missing 1076 *
1008 # 1031 # 1054 * 1077 *
1009 # 1032 # 1055 * 1078 *
1010 # 1033 # 1056 * 1079 *
1011 # 1034 # 1057 * 1080 *
1012 # 1035 # 1058 * 1081 *
1013 # 1036 # 1059 * 1082 *
1104 # 1037 # 1060 0.01 1083 *
1015 # 1038 # 1061' * 1084 *
1016 # 1039 # 1062 * 1085 *
1017 # 1040 # 1063 * 1086 *
1018 # 1041 * 1064 * 1087 *-
1019 # 1042 * 1065 * 1088 *
1020 # 1043 * '1066 * 1089 *
1021 # 1044 * 1067 * 1090 *
1022 # 1045 * 1068 * 1091 *
1023 # 1046 Missing 1069 Missing 1092 *

 

 

 

 

 

 

 

 

 

# Pesticide has not been applied

* Not Detected

 

74

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B1 Bayleton Data cont.
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(PPm) (PPm) (PPm) (9m)
2001 # 2024 # 2047 * 2070 *
2002 # 2025 # 2048 * 2071 *
2003 # 2026 # 2049 * 2072 *
2004 # 2027 # 2050 0.01 2073 *
2005 # 2028 # 2051 * 2074 *
2006 # 2029 # 2052 * 2075 *
2007 # 2030 # 2053 Missing 2076 *
2008 # 2031 # 2054 * 2077 *
2009 # 2032 # 2055 * 2078 *
2010 # 2033 # 2056 * 2079 *
2011 # 2034 # 2057 * 2080 *
2012 # 2035 # 2058 * 2081 *
2013 # 2036 # 2059 * 2082 *
2104 # 2037 # 2060 0.01 2083 *
2015 # 203 8 # 2061 0.01 2084 *
2016 # 2039 # 2062' * 2085 *
2017 # 2040 # 2063 * 2086 *
2018 # 2041 * 2064 * 2087 *
2019 # 2042 * 2065 * 2088 *
2020 # 2043 * 2066 * 2089 *
2021 # 2044 * 2067 * 2090 *
2022 # 2045 * 2068 * 2091 *
2023 # 2046 Missing 2069 Missing 2092 *

 

 

 

 

 

 

 

 

 

 

7S

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B2 Isazofos Residue Data
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(PPm) (Ppm) (Ppm) (99m)
1001 # 1024 * 1047 * 1070 *
1002 # 1025 * 1048 * 1071 *
1003 * 1026 * 1049 * 1072 *
1004 * 1027 * 1050 * 1073 *
1005 * 1028 * 1051 * 1074 *
1006 * 1029 * 1052. * 1075 *
1007 * 1030 * 1053 Missing 1076 *
1008 * 1031 * 1054 * 1077 *
1009 * 1032 * 1055 * 1078 *
1010 * 1033 * 1056 * 1079 *
1011 * 1034 * 1057 * 1080 *
1012 * 1035 * 1058 * 1081 *
1013 * 1036 * 1059 * 1082 *
1104 * 1037 * 1060 * 1083 *
1015 * 1038 * 1061 * 1084 *
1016 * 1039 * 1062 * 1085 *
1017 * 1040 * 1063 * 1086 *
1018 * 1041 * 1064' * 1087 *
1019 * 1042 * 1065 * 1088 *
1020 * 1043 * 1066 * 1089 *
1021 * 1044 * 1067 * 1090 *
1022 * 1045 * 1068 * 1091 *
1023 * 1046 Missing 1069 Missing 1092 *
# Pesticide has not been‘applied * Not Detected

 

76

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B2 Isazofos Data cont.
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(PPm) (PPm) (PW) (9991)
2001 # 2024 * 2047 * 2070 *
2002 # 2025 * 2048 * 2071 *
2003 * 2026 * 2049 * 2072 *
2004 * 2027 * 2050 * 2073 *
2005 * 2028 * 2051 * 2074 *
2006 * 2029 * 2052 * 2075 *
2007 * 2030 * 2053 Missing 2076 *
2008 * 2031 * 2054. * 2077 *
2009 * 2032 * 2055 * 2078 *
2010 "‘ 2033 * 2056 * 2079 *
2011 * 2034 * 2057 * 2080 *
2012 * 2035 * 2058 * 2081 *
2013 * 2036 * 2059 * 2082 *
2104 * 2037 * 2060 * 2083 *
2015 * ' 2038 * 2061 * 2084 *
2016 * 2039 * 2062 * 2085 *
2017 * 2040 * 2063 * 2086 *
2018 * 2041 * 2064 * 2087 *
2019 * 2042 * 2065 * 2088 *
2020 * 2043 * 2066' * 2089 *
2021 * 2044 * 2067 * 2090 *
2022 * 2045 * 2068 * 2091 *
2023 * 2046 Missing 2069 Missing 2092 *

 

77

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B3 Fenarirnol Residue Data
Sample # Conc Sample # Cone Sample # Conc Sample # Conc
(13m) (99m) (PPm) (9m)
1001 # 1024 # 1047 * 1070 *
1002 # 1025 # 1048 * 1071 *
1003 # 1026 # 1049 * 1072 *
1004 # 1027 # 1050 * 1073 *
1005 # 1028 # 1051 * 1074 *
1006 # 1029 # 1052 * 1075 *
1007 # 1030 # 1053 Missing 1076 *
1008 # 1031 # 1054 * 1077 *
1009 # 1032 # 1055 * 1078 *
1010 # 1033 # 1056. * 1079 *
1011 # 1034 * 1057 * 1080 *
1012 # 1035 * 1058 * 1081 *
1013 # 1036 * 1059 * 1082 *
1104 # 1037 * 1060 * 1083 "'
1015 # 1038 * 1061 * 1084 *
1016 # 1039 * 1062 * 1085 *
1017 # 1040 * 1063 * 1086 *
1018 # 1041 * 1064 * 1087 *
1019 # 1042 * 1065 * 1088 *
1020 # 1043 * 1066 * 1089 *
1021 # 1044 * 1067 * 1090 *
1022 # 1045 * 1068' * 1091 * ,
1023 # 1046 Missing 1069 Missing 1092 *
# Pesticide has not been applied * Not Detected

 

78

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B3 F enarimol Data cont.
Sample # Cone Sample # Cone Sample # Conc Sample # Conc
(PPm) (MM) (9919) (Ppm)
2001 # 2024 # 2047 * 2070 *
2002 # 2025 # 2048 * 2071 *
2003 # 2026 # 2049 * 2072 *
2004 # 2027 # 2050‘ * 2073 *
2005 # 2028 # 2051 * 2074 *
2006 # 2029 # 2052 * 2075 *
2007 # 2030 # 2053 Missing 2076 *
2008 # 2031 # 2054 * 2077 *
2009 # 2032 # 2055 * 2078 *
2010 # 2033 # 2056 * 2079 *
2011 # 2034 * 2057 * 2080 *
2012 # 203 5 * 2058 * 2081 *
2013 # 2036 * 2059 * 2082 *
2104 # 2037 * 2060 * 2083 *
2015 # 203 8 * 2061. * 2084 *
2016 # 203 9 * 2062 * 2085 *
2017 # 2040 * 2063 * 2086 *
2018 # 2041 * 2064 * 2087 *
2019 # 2042 * 2065 * 2088 *
2020 # 2043 * 2066 * 2089 *
2021 # 2044 * 2067 * 2090 *
2022 # 2045 * 2068 * 2091 *
2023 # 2046 Missing 2069 7 Missing 2092 *

 

 

 

 

 

 

 

 

 

 

79

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B4 Propiconazole Residue Data
Sample # Conc Sample # Conc Sample # Cone Sample # Conc
(PPm) (ppm) - (Ppm) Cm)
1001 # 1024 # 1047 * 1070 *
1002 # 1025 # 1048 * 1071 *
1003 # 1026 # 1049 * 1072 *
1004 # .1027 # 1050 * 1073 *
1005 # 1028 # 1051 * 1074 *
1006 # 1029 # 1052 * 1075 *
1007 # 1030 # 1053 Missing 1076 *
1008 # 1031 # 1054 * 1077 *
1009 # 1032 # 1055 * 1078 *
1010 # 1033 # 1056 * 1079 *
1011 # 1034 # 1057 * 1080 *
1012 # 1035 # 1058 * 1081 *
1013 # 1036 # 1059 * 1082 *
1104 # 1037 * 1060 * 1083 *
1015 # 1038 * 1061 * 1084 *
1016 # 1039 * 1062 * 1085 *
1017 # 1040 * 1063 * 1086 *
1018 # 1041 * 1064‘ * 1087 *
1019 # 1042 * 1065 * 1088 *
1020 # 1043 * 1066 * 1089 *
1021 # 1044 * 1067 * 1090 *
1022 # 1045 * 1068 * 1091 *
1023 # 1046 Missing 1069 Missing 1092 *
# Pesticide has not been applied * Not Detected

 

80

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B4 Propiconazole Data cont.
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(99m) (91319) (99m) (99m)
2001 # 2024 # 2047 * 2070 *
2002 # 2025 # 2048 * 2071 *
2003 # 2026 # 2049 * 2072 *
2004 # 2027 # 2050 * 2073 *
2005 # 2028 # 2051 * 2074 *
2006 # 2029 ‘# 2052 * 2075 *
2007 # 2030 # 2053 Missing 2076 *
2008 # 2031 # 2054 * 2077 *
2009 # 2032 # 2055 * 2078 *
2010 # 2033 # 2056 * 2079 *
2011 # 2034 # 2057 * 2080 *
2012 # 2035 # 2058 * 2081 *
2013 # 2036 # 2059 * 2082 *
2104 # 2037 * 2060 * 2083 *
2015 # 2038 * 2061 * 2084 *
2016 # 2039 * 2062 * 2085 *
2017 # 2040 * 2063 * 2086 *
2018 # 2041 * 2064 * 2087 *
2019 # 2042 * 2065 * 2088 *
2020 # 2043 * 2066 * 2089 *
2021 # 2044 * 2067 * 2090 *
2022 # 2045 * 2068 * 2091 *
2023 # 2046 Missing 2069 Missing 2092 *

 

 

 

 

 

 

 

 

 

 

81

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B5 Chlorothalonil Residue Data
Sample # Conc Sample # Conc Sample # Cone Sample # Conc
(Ppm) (9991) (WITH) (rpm)
1001 # 1024 * 1047 * 1070 *
1002 # 1025 * 1048 * 1071 *
1003 # 1026 * 1049 * 1072 *
1004 * 1027 * 1050 * 1073 *
1005 * 1028 * 1051 *- 1074 *
1006 * 1029 * 1052 * 1075 *
1007 * 1030 * 1053 Missing 1076 *
1008 * 1031 * 1054 * 1077 *
1009 * 1032 * 1055 * 1078 *
1010 * 1033 * 1056' * 1079 *
1011 * 1034 * 1057 * 1080 *
1012 * 1035 * 1058 * 1081 *
1013 * 1036 * 1059 * 1082 *
1104 * 1037‘ * 1060 * 1083 *
1015 * 1038 * 1061 * 1084 *
1016 * 1039 * 1062 * 1085 *
1017 * 1040 * 1063 * 1086 *
1018 * 1041 * 1064 * 1087 *
1019 * 1042 * 1065 * 1088 *
1020 * 1043 * 1066 * 1089 *
1021 * 1044 * 1067 * 1090 *
1022 * 1045 * 1068' * 1091 "f
1023 * 1046 Missing 1069 Missing 1092 *
# Pesticide has not been applied * Not Detected

 

82

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B5 Chlorothalonil Data cont.
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(ppm) (ppm) _ (ppm) (ppm)
2001 # 2024 * 2047 * 2070 *
2002 # 2025 * 2048 * 2071 *
2003 # 2026 * 2049 * 2072 *
2004 * 2027 * 2050 * 2073 *
2005 * 2028 * 2051 * 2074 *
2006 * 2029 * 2052 * 2075 *
2007 * 2030 * 2053' Missing 2076 *
2008 * 2031 * 2054 , * 2077 *
2009 * 2032 * 2055 * 2078 *
2010 * 2033 * 2056 * 2079 *
2011 * 2034 * 2057 * 2080 *
2012 * 203 5 * 2058' * 2081 *
2013 * 2036 * 2059 * 2082 *
2104 * 2037 * 2060 * 2083 *
2015 * 203 8 * 2061 * 2084 *
2016 * 2039 * 2062 * 2085 *
2017 * 2040 * 2063 * 2086 *
2018 * 2041 * 2064 -* 2087 *
2019 * 2042 * 2065 "‘ 2088 *
2020 * 2043 * 2066 * 2089 *
2021 * 2044 * 2067 * 2090 *
2022 * 2045 * 2068 * 2091 *
2023 * 2046 lVIissing 2069 Missing 2092 *

 

 

 

 

 

 

83

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B5 Chlorothalonil Data cont.
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(Ppm) (Ppm) (9m) (9m)
3001 # 3024 * 3047 * 3070 *
3002 # 3025 * 3048. * 3071 *
3003 # 3026 * 3049 * 3072 *
3004 * 3027 * 3050 * 3073 *
3005 * 3028 * 3051 * 3074 *
3006 * 3029 * 3052 * 3075 *
3007 * 3030 * 3053 Missing 3076 *
3008 * 3031 * 3054 * 3077 *
3009 * 3032 * 3055 * 3078 *
3010 * 3033 * 3056 * 3079 *
3011 * 3034 * 3057 * 3080 *
3012 * 3035 * 3058 * 3081 *
3013 * 3036 * 3059 * 3082 *
3104 * 3037 * 3060 * 3083 *
3015 * 3038 * 3061 * 3084 *
3016 * 3039 * 3062 * 3085 *
3017 * 3040 * 3063 * 3086 *
3018 * 3041 * 3064 * 3087 *
3019 * 3042 * 3065 * 3088 *
3020 * 3043 * 3066 * 3089 *
3021 * 3044 * 3067 * 3090 *
3022 * 3045 * 3068 * 3091 *
3023 * 3046 * 3069 Missing 3092 *

 

 

 

 

 

 

 

 

 

 

84

‘Chlorothalonil Data cont.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B5
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(ppm) ~ (ppm) (ppm) (ppm)
4001 # 4024 * 4047 * 4070 *
4002 # 4025 * 4048 * 4071 *
4003 # 4026 * 4049 * 4072 *
4004 * 4027 * 4050 * 4073 *
4005 * 4028 * 4051 * 4074 *
4006 * 4029 * 4052- *p 4075 *
4007 1* 4030 * 4053 Missing 4076 *
4008 * 4031 * 4054 * 4077 *
4009 * 4032 * 4055 * 4078 *
4010 * 4033 * 4056 * 4079 *
4011 * 4034 * 4057 * 4080 *
4012 * 4035 * 4058 * 4081 *
4013 * 4036 * 4059 * 4082 *
4104 * 4037 * 4060 * 4083 *
4015 * 4038 * 4061 * 4084 *
4016 * 4039 * 4062 * 4085 *
4017 * 4040 * 4063 * 4086 *
4018 * 4041 * 4064 * 4087 *
4019 * 4042 * 4065 * 4088 *
4020 * 4043 * 4066 * 4089 *
4021 * 4044 * 4067 * 4090 *
4022 * 4045 * 4068 * 4091 *
4023 * 4046 Missing 4069 Missing 4092 *

 

 

 

 

 

 

 

 

 

 

85

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B6 2,4-D Residue Data
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(ppm) (ppm) (ppm) (ppm)
1001 # 1024 * 1047 * 1070 *
1002 # 1025 * 1048 * 1071 "‘
1003 # 1026 * 1049 * 1072 *
1004 # 1027 * 1050 * 1073 *
1005 # 1028 * 1051 * 1074 *
1006 # i 1029 * 1052 * 1075 *
1007 # 1030 * 1053 Missing 1076 *
1008 # 1031 * 1054 * 1077 *
1009 * 1032 * 1055 * 1078 *
1010 * 1033 * 1056 * 1079 *
1011 * 1034 * 1057 * 1080 *
1012 * 1035 * 1058 * 1081 *
1013 "‘ 1036 * 1059 * 1082 *
1104 "‘ 1037 * 1060 * 1083 *
1015 * 1038 * 1061 * 1084 *
1016 * 1039 * 1062 * 1085 "'
1017 * 1040 * 1063 * 1086 *
1018 * 1041 * 1064 * 1087 *
1019 * 1042 * 1065 * 1088 *
1020 * 1043 * 1066 * 1089 _ *
1021 * 1044 * 1067 * 1090 *
1022 * 1045 * 1068 * 1091 *
1023 * 1046 Missing 1069 Missing 1092 *

 

 

 

 

 

 

 

 

 

# Pesticide has not been applied

* Not Detected

 

86

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B6 2,4—D Data cont.
Sample # Conc Sample # Conc Sample # Conc Sample # Cone
(ppm) (ppm) (ppm) (ppm)
2001 # 2024 * 2047 * , 2070 *
2002 # 2025 * 2048 * 2071 *
2003 # 2026 * 2049 * 2072 *
2004 # 2027 * 2050 * 2073 *
2005 # 2028 * 2051. * 2074 *
2006 # 2029 * 2052 * 2075 *
2007 # 2030 * 2053 Missing 2076 *
2008 # 2031 * 2054 * 2077 ‘ 5*
2009 * 2032 * 2055 * 2078 *
2010 * 2033 * 2056 * 2079 *
2011 * 2034 * 2057 * 2080 *
2012 * 2035 * 2058 * 2081 *
2013 * 2036 * 2059 * 2082 *
2104 * 2037 * 2060 * 2083 *
2015 * _ 2038 * 2061 * 2084 *
2016 * 2039 * 2062 * 2085 *
2017 * 2040 * 2063 * 2086 *
2018 * 2041 * 2064 * 2087 *
2019 * 2042 * 2065 * 2088 *
2020 * 2043 * 2066 * 2089 *
2021 * 2044 * 2067 * 2090 *
2022 * 2045 * 2068 * 2091 *
2023 * 2046 Missing 2069 Missing 2092 *

 

 

 

 

 

 

 

 

 

 

87

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B7 Dicamba Residue Data
Sample # Conc Sample # Conc Sample # I Conc Sample # Conc
(ppm) (ppm) (ppm) (ppm)
1001 # 1024 * 1047 * 1070 *
1002 # 1025 * 1048 * 1071 *
1003 # 1026 * 1049 * 1072 *
1004 # 1027 * 1050 * 1073 *
1005 # 1028 * 1051 * 1074 *
1006 # 1029 * 1052 * 1075 *
1007 # 1030 * 1053 Missing 1076 *
1008 # 1031 * 1054 * 1077 *
1009 * 1032 * 1055 * 1078 *
1010 * 1033 * 1056 * 1079 *
1011 * 1034 * 1057 * 1080 *
1012 * 1035 * 1058 * 1081 *
1013 * 1036 * 1059 * 1082 *
1104 * 1037 * 1060 * 1083 *
1015 * 1038 * 1061 * 1084 5*
1016 * 1039 * 1062 * 1085 *
1017 * 1040 * 1063 * 1086 *
1018 * 1041 * 1064 * 1087 *
1019 * 1042 * 1065 * 1088 *
1020 * 1043 * 1066 * 1089 *
1021 * 1044 * 1067 * 1090 *
1022 * 1045 * 1068 * 1091 *
1023 * 1046 Missing 1069 Missing 1092 *

 

 

 

 

 

 

 

 

 

# Pesticide has not been applied

* Not Detected

 

88

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B7 Dicamba Data cont.
Sample # Cone Sample # Conc Sample # Conc Sample # Conc
(ppm) (ppm) (ppm) (ppm)
2001 # 2024 * 2047 * 2070 *
2002 # 2025 * 2048 * 2071 *
2003 # 2026 * 2049 * 2072 *
2004 # 2027 * 2050 * 2073 *
2005 # 2028 * 2051 * 2074 *
2006 # 2029 * 2052 * 2075 *
2007 # 2030 * 2053 Missing 2076 *
2008 # 2031 * 2054 * 2077 *
2009 * 2032 * 2055 * 2078 *
2010 * 2033 * 2056 * 2079 *
2011 * 2034 * 2057 * 2080 *
2012 * 2035 * 2058 * 2081 ' *
2013 * 2036 * 2059 * 2082 *
2104 * 2037 * 2060 * 2083 *
2015 * 203 8 * 2061 * 2084 *
2016 * 2039 * 2062 * 2085 *
2017 * 2040 * 2063 * 2086 *
2018 * 2041 * 2064 * 2087 *
2019 * 2042 * 2065 * 2088 *
2020 * 2043 * 2066. * 2089 *
2021 * 2044 * 2067 * 2090 *
2022 * 2045 * 2068 * 2091 *
2023 * 2046 Missing 2069 Missing 2092 *

 

 

 

 

 

 

 

 

 

 

89

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B8 Metalaxyl Residue Data
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(ppm) (Ppm) (PM) (PM)
1001 # 1024 # 1047 * 1070 *
1002 # 1025 # 1048 * 1071 *
1003 # 1026 # 1049 * 1072 *
1004 # 1027 # 1050 * 1073 *
1005 # 1028. # 1051 * 1074 *
1006 # 1029 # 1052 * 1075 *
1007 # 1030 # 1053 Missing 1076 *
1008 # 1031 # 1054 * 1077 *
1009 # 1032 # 1055 * 1078 *'
1010 # 1033 # 1056 * 1079 *
1011 # 1034 # 1057 * 1080 *
1012 # 1035 # 1058 * 1081 *
1013 # 1036 # 1059 * 1082 *
1104 # 1037 # 1060 * 1083 *
1015 # 1038 # 1061- * 1084 *
1016 # 1039 # 1062 * 1085 *
1017 # 1040 # 1063 * 1086 *
1018 # 1041 # 1064 * 1087 *
1019 # 1042 # 1065 * 1088 *
1020 # 1043 # 1066 * 1089 *
1021 # 1044 * 1067 * 1090 *
1022 # 1045 * 1068 * 1091 *
1023 # 1046 Missing 1069 Missing 1092 *

 

 

 

 

 

 

 

 

 

# Pesticide has not been applied

* Not Detected

 

90

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B8 Metalaxyl Data cont.
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(ppm) (ppm) (ppm) (ppm)
2001 # 2024 # 2047 * 2070 *
2002 # 2025 # 2048 * 2071 *
2003 # 2026 # 2049‘ * 2072 *
2004 # 2027 # 2050 * 2073 *
2005 # 2028 # 2051, * 2074 *
2006 # 2029 # 2052 * 2075 *
2007 # 2030 # 2053 Missing 2076 *
2008 # 2031 # 2054 * 2077 *
2009 # 2032 # 2055 * 2078 *
2010 # ' 2033 # 2056 * 2079 *
2011 # 2034 # 2057 * 2080 *
2012 # 2035 # 2058 * 2081 *
2013 # 2036 # 2059 * 2082 *
2104 # 2037 # 2060 * 2083 *
2015 # 2038 # 2061 * 2084 *
2016 # 2039 # 2062 * 2085 *
2017 I # 2040 # 2063' * 2086 *
2018 # 2041 # 2064 * 2087 *
2019 # 2042 # 2065 * 2088 *
2020 # 2043 # 2066 * 2089 *
2021 # 2044 * 2067 * 2090 *
2022 # 2045 * 2068 * 2091 *
2023 # 2046 Missing 2069 Missing 2092 *

 

 

 

 

 

 

 

 

 

 

91

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B8 Metalaxyl Data cont.
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(ppm) (ppm) (ppm) (ppm)
3001 # 3024 # 3047 * 3070 *
3002 # 3025 # 3048 * 3071 *
3003 # 3026 # 3049 * 3072 *
3004 # 3027 # 3050 * 3073 *
3005 # 3028 # 3051 * 3074 *
3006 # 3029 # 3052 * 3075 *
3007 # 3030 # 3053 Missing 3076 *
3008 # 3031 # 3054 * 3077 *
3009 # 3032 # 3055 * 3078 *
3010 # 3033 # 3056 * 3079 *
3011 # 3034 # 3057 * 3080 *
3012 # 3035 # 3058 * 3081 *
3013 # 3036 # 3059 * 3082 *
3104 # 3037 # 3060 * 3083 *
3015 # 3038 # 3061 * 3084 *
3016 # 3039 l # 3062 * 3085 *
3017 # 3040 * 3063 * 3086 *
3018 # 3041 * 3064 * 3087 *
3019 # 3042 * 3065. * 3088 *
3020 # 3043 * 3066 * 3089 *
3021 # 3044 * 3067 * 3090 *
3022 # 3045 * 3068 * 3091_ *
3023 # 3046 * 3069 Missing 3092 *

 

 

 

 

 

 

 

 

 

 

92

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B8 Metalaxyl Data cont.
Sample # Conc Sample # Conc Sample # Conc Sample # Conc
(ppm) (ppm) (ppm) (ppm)
4001 # 4024 # 4047 * 4070 *
4002 # 4025 # 4048 * 4071 *
4003 # 4026 # 4049 * 4072 *
4004 # 4027 # 4050 *. 4073 *
4005 # 4028 # 4051 * 4074 *
4006 # 4029 # 4052 * 4075 *
4007 # 4030 # 4053 Missing 4076 *
4008 # 4031 # 4054 * 4077 *
4009 # ‘ 4032 # 4055 * 4078 *
4010 # 4033 # 4056 * 4079 *
4011 # 4034 # 4057 * 4080 *
4012 # 4035 # 4058 * 4081 , *
4013 # 4036 # 4059 * 4082 *
4104 # 4037 # 4060 * 4083 *
4015 # 4038 # ' 4061 * 4084 *
4016 # 4039 ' # 4062 * 4085 *
4017 # 4040 * 4063 * 4086 *
4018 # 4041 * 4064 * 4087 *
4019 # 4042 -* 4065 * 4088 *
4020 # 4043 * 4066 * 4089 *
4021 # 4044 * 4067 * 4090 *
4022 # 4045 * 4068' * 4091 *
4023 # 4046 Missing 4069 Missing 4092 *

 

 

 

 

 

 

 

 

 

 

 

 

i i - - u ,u. m m .u..0. .u
it::JUE.E.31.0.00.anaA;iflflfliiflfl$$w<iLJ\J\A\A\S\
-_ 1:1 1 I/_€_c:(2(_(_(;\1_\-_h: .

93

Table B9-Rainfall and Irrigation Data

 

Rainfall &

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Rainfall 87.
Collection Date/Sample # Irrigation Collection Date/Sample # Irrigation
May 5, 1991/1 11.1 September 4/47 5.16
May 17/2 2.9 September 8/48 2.57
June 12/3 11.43 September 10/49 2.59
July 22/4 12.78 September 15/50 0.03
August 17/5 14.99 September 29/51 4.06
‘ August 23/6 4.95 October 15/52 5.56
August 29/7 ‘ 3.12 October 16/53 1.19
August 30/8 0.48 October 26/54 0.43
September 3/9 3.93 November 3/55 3.3
September 16/10 2.6 November 12/56 2.67
October 22/11 8.35 November 13/57 1.55
October 26/12 2.01 November 20/58 0.05
October 27/13 1.7 November 23/59 2.84
October 30/14 0.38 November 29/60 0.33
November 8/15 0.69 December 14/61 0.99
November 20/16 3.68 December 28/62 0.84
November 23/17 0.03 ‘ December 31/63 3.4
December 3/18 3.99 January 4, 1993/64 3.53
December 12/19 1.09 January 4/65 0
December 18/20 1.42 January 8/66 0.48
January 3, 1992/21 0.38 January 29/67 4.17
January 22/22 0 March 9/68 3.63
February 21/23 2.34 April 5/70 4.95
February 27/24 0.48 April 13/71 1.04
March 7/25 0.91 April 21 I72 7.87
March 18/26 1.32 April 22/73 0.51
March 25/27 0 May 11/74 4.22
March 27/28 0.61 June 8/75 9.3
April 4/29 0.56 June 9/76 1.37
Apn'l 10/30 1.65 June 24/77 5.38
April 16/31 2.77 July 9/78 3.28
April 21/32 1.35 July 27/79 11.28
April 24/33 2.69 July 30/80 2.06
A ril 25/34 1.57 August 5/81 0.79
April 27/35 0.94 August 17/82 4.06
May 6/36 1.3 August 24/83 2.21
June 8/37 12.12 September 14/84 8.94
June 17/38 0 September 21/85 2.39
July 7/39 6.45 September 28/86. 3.33
July 14.40 7.37 October 7/87
July 16/41 1.7 October 19/88
July 20/42 1.63 October 22/89
July 29/43 2.06 November 16/90 1.27 '
July 31/44 4.32 December 9/91 3.02
August 4/45 0 December 23/92 0.61
August 13/46 3.58 Sub Total 127.25
Sub Total 149.72 Total 276.97

 

 

94

Table BIO-Volume of Water Collected

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Collection Date/Sample # Lysimeter 1 (ml) Lysimeter 2 (ml Lysimeter 3 (ml Lysimeter‘l (ml)
May 5, 1991/1 8144 9083
May 17/2 4961 6728
June 1213 9638 7448
July 22/4 6931 311
August 17/5 9247 3242
August 23/6 3098 4956’
August 29/7 12021 10987
August 30/8 5365 6420
September 3/9 29438 33688
September 16/10 4367 6600
October 22/11 1520 8160
October 26/12 2421 1509
October 27/13 9633 8618
October 30/14 6241 9236
November 8/15 7879 9459 10352 10217
November 20/16 13887 10081 8394 9978
November 23/17 11497 15062 16132 15611
December 3/18 37006 37053 26769 24616
December 12/19 42017 46235 12473 17780
December 18/20 12687 13685 12776 13117
January 3, 1992/21 17008 16254 11387 13784
January 22/22 13363 14904 16284 14682
February 21/23 25963 31760 5284 16881
February 27/24 11665 11568 10980 8157
March 7/25 5137 5969 7319 4864
March 18/26 28553 22315 ' 20412 21236
7 March 25/27 9717 10127. 11429 13247
March 27/28 3508 13169 2630 8307
April 4/29 9280 12469 9378 11690
April 10/30 9316 12469 5661 6500
April 16/31 8520 8985 6644 5599
April 21/32 12490 12419 10251 9711
April 24/33 17734 16418 11543 13020
April 25/34 12844 12991 12977 12556
April 27/35 12682 15187 15606 15240
May 6/36 11189 12478 13467 15240
June 8/37 23023 17282 25968 16109
June 17/38 5454 8487 13641 7745
July 7/39 317 529' 1049 629
July 14,40 27312 28283 7601 778
July 16/41 19338 25623 20949 16623
July 20/42 9836 10724 8482 8478
July 29/43 10025 10464 11475 8474
July 31/44 19286 14904 11037 10668
August 4l45 8765 13321 15621 13444
August 13/46 8802 7044 4242 3495
September 4/47 13959 17586 929 4641
September 8/48 32286 36588 32379 32502
1R'IQR 1110527 11014 4on1n

 

 

.Qpntomhnr 1 “I210

Table 1

W

Septemb
68663?
93129:
Novembe
Novembe
Novembe
,W
Novembé
(Novemg
Decembe
Decembe
Decembe
January 1
My;
@999:
11199 9
A901 5171
April 22”
x
June 8/7
\
June 9/7
N
June 24/
\‘
July 9/75
\
July 27/7
My 30/&
August 5
AUgust 1
AUgUst 2
Septemt
Septemt
OQOber

 

95

Table lO—Volume of Water Collected cont.

 

Collection Date/Sample #

Lysimeter1 (ml)

Lysimeter 2 (ml)

Lysimeter 3 (ml)

Lysimeter 4 (ml)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

September 15/50 6610 10155 12149 10967
September 29/51 8994 10616 6128 9740
October 15/52 9112 8151 6276 6576
October 16/53 18988 19289 17672 18247
October 26/54 10742 15411 17281 15070
November 3/55 15878 13096 13701 13963
November 12/56 24328 22830 21310 20238
November 13/57 12925 16885 17761 17950
November 20/58 10286 13492 15020 13468
November 23/59 23255 ' 19315 17838 17946
November 29/60 9703 11648 13281 11751
December 14/61 8401 9366 8281 7877
December 28/62 9074 10127 6316 5897
December 31/63 19254 17348 12931 17368
January 4, 1993/64 13096 12491' 11557 10498
January 4/65 10263 10425 9992 10264
JanuaryS/GG 15412 18238 19163 17608
Emery 29/67 47655 51901 16657 14325
March 9/68 - 7145 19271 7700 19158
April 5/70 14308 19148 12614 13006
April 13/71 9700 11332 9966 8527
April 21/72 19247 19274 19681 18304
April 22/73 9367 14516 13695 11645
May 11/74 13763 16586 14719 14389
June 8/75 11896 6378 3980 16927
June 9/76 8713 9184 8521 8558
June 24/77 41264 46235 44619 47069
July 9/78 4246 6643 5847 6805
July 27/79 36262 36306 36757 36141
July 30/80 19543 19622 16886 14269
August 5/81 10020 16062 9385 19151
August 17/82 15040 19156 14194 20842
August 24/83 26583 30667 23139 27756
September 14/84 10949 14324 10981 11392
September 21/85 40518 37563 31365 40923
September 28/86 23618 26848 23724 25589
October 7/87 9954 13118 15787 14023
October 19/88 26224 23834 20245 23948
October 22189 8976 9484 8744 8421
November 16/90 6017 10306 11577 11235
December 9/91 17498 15730 14486 14789
December 23/92 5650 7244 8125 8019
Total 1311243 1422780 1053513 1099307
Average 14409.26374 15634.94505 13681 .98701 14276.71429

 

 

APPENDIX C--STANDARD OPERATING PROCEDURES

96

QUALITY ASSURANCE
STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #: 1 By: Chris Vandervoort Date: 07Feb92
0.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

0.0 QA/QC Golf Course Project

0.0 Method Validation
1.Spike a control with 2 -5 times the limit of quantification.
2. Run a solvent blank to 100k for interferences in the
chromatogram with the analyte of interest.
3. Run 10 % of the samples in duplicate to assure repeatability.
4. Run a standard curve and do a least squares regression for a line
for quantification of samples.
5. Place one liter of water in refrigerator. Spike with about 1 ppm
of the pesticide of interest. Run recovery on GC.
Approved: Date:
Matthew Zabik, Laboratory Director

 

97

QUALITY ASSURANCE

STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #: 1 By: C. Vandervoort Date: 30Apr92
1.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

1.0 Determination of Chlorothalonil in Water

1.0 Extraction of Chlorothalonil

1.

.5"?

Approved:

Weigh 100 g of water and place in 250 ml
separatory funnel, add 20 g of NaCl,
solubilization.

Extract 3 times with 20 ml of hexane, each
time shake for three minutes and combine
extracts, then with small amount of hexane

‘ rinse separatory funnel and transfer to hexane

extracts.

Reduce the volume of extracts to about 1 ml, in
Turbo-Vap. Never let extracts go to dryness.
Bring the final volume to 5 ml with hexane.
Analyze with electron capture detector and 30
m DB-5 capillary column equipped GC.

Date:

 

Matthew Zabik, Laboratory Director

98

QUALITY ASSURANCE

STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #: 1 By: C. Vandervoort Date: 30Apr92
2.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

2.0

Determination of Chlorpyrifos in Grass

2.0 Extraction of Chlorpyrifos

Approved:

1.

U.)

Weigh 10 g of and homogenize with 100 ml
acetone for 5-10 minutes. Filter with a
sintered glass funnel with vacuum. Repeat
with fresh 100 ml of acetone and combine
extracts.

Roto-vap to dryness and add 20 ml of hexane.
Put through 2 g of silica-gel 70-230 mesh (oven
dried at 110° C for 4 hours) with a glass wool
pledget. Rinse flask with 15 ml of hexane
twice and add to the column.

Turbo-Vap to dryness and add 4 ml of acetone.

Analyze with GC.

Date:

 

Matthew Zabik, Laboratory Director

99

QUALITY ASSURANCE
STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #: 1 By: C. Vandervoort Date: 30Apr92
3.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

3.0 Determination of Clopyralid in Grass

3.0 Extraction of Clopyralid
l. Weigh 10 g of and place in 250 ml
Erlenmeyer flask and shake for 5 minutes,
with 150 ml of KOH.

2. Transfer to separatory funnel. Add 100 ml of

diethyl ether, 5 g NaCl and 20 ml of 4 M H2S04.
Shake and separate the ether from the aqueous
layer and save ether layer , and repeat ether
extraction with fresh ether and combine ether
extracts. Put through a bed of NaZSO4.

3. Reduce the volume of extracts to about 1 ml, in

Turbo-Vap.

4. Esterification with diazomethane. Add ca. 2 ml
of diazomethane to sample til yellow color
remains for 1 hour.

5. Analyze with electron capture detector and 30

m DB-5 capillary column equipped GC.

Approved: ' Date:
Matthew Zabik, Laboratory Director

 

100

QUALITY ASSURANCE

STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #2 1 By: Chris Vandervoort Date: 13-Apr-92
4.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

4.0 Determination of Dicamba in Water

4.0 Extraction and clean-up of Dicamba

1.

Approved:

Weigh 10 g of water and place in a 125 mL
separatory funnel: acidify to pH 1 by adding 5

mL of 10 % H2804, Extract 3 times with 25 mL of
diethyl ether and combine ether extracts.

Reduce the volume of extract to about 10

mL.

Prepare a Celite column. To 100 g of Celite

add 40 mL of bufier solution. The bufler

solution is prepared by mixing equal volumes of

2M sodium dihydrogen phosphate and 2M potassium '
monohydrogen phosphate. Store the ether

for one week then discard. Equilibrate 1.5 1

of diethyl ether with 100 mL of phosphate

buffer shake and discard aqueous portion. Add

15 g of buffered Celiteto a column with periodic

draining and addition of equilibrated ether to keep packing
covered. Add extract and elute with 265 mL of equilibrated
ether. Reduce in volume to about 2 mL.

Esterification with diazomethane. Add ca. 2 mL
of diazomethane to sample til yellow color
remains for 1°' Then reduce volume to < 0.5 mL.

' ECD-GC analysis

Date:

 

101

Matthew Zabik, Laboratory Director

102

QUALITY ASSURANCE

STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #: 1 By: Chris Vandervoort Date: 07Feb92
5.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

5.0 Determination of F enarimol in Water

5.0 Extraction of F enarimol

l.

3.

Weigh a 100 g sample of water add 50 ml of 10%
NaCl and extract twice with 40 mL of methylene
chloride, combine extracts in a drying flask.
Turbo-Vap to dryness at 40-45 ° C.

5.1 Clean-up of samples

1.

Approved:

Prepare an alumina column with

To a 12 mm i.d. column with a glass wool
pledget rinse with 15 mL of methylene chloride
and then add 13 +/- 0.5 g alumina, rinse with
10 mL of methylene chloride. Add 1.7 cm of
anhydrous sodium sulfate, rinse with 10 mL of
methylene chloride. Drain methylene chloride
down to the top of the bed level of the column
and add sample. Add 40 mL 9:1 methylene
chloridezethyl acetate, discard eluate.

Add 120 mL 99:1 methylene chloridezmethanol,
collect and reduce to dryness in turbo-vap.
Bring to volume with hexane for GC analysis.

Date:

 

Matthew Zabik, Laboratory Director

103

QUALITY ASSURANCE

STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #: 1 By: Chris Vagglervoort Date: 30Apr92
6.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

6.0 Determination of Isazofos in Water

6.0 Extraction of Isazofos

l.

.U'P

Approved:

Weigh 100 g of water and place in 250 mL
separatory funnel, add 20 g of NaCl,
solubilization.

Extract 3 time with 20 mL of Chloroform, .each
time shake for three minutes and combine
extracts, then with small amount of chloroform
rinse separatory funnel and transfer to

, chloroform extracts.

Reduce the volume of extracts to about 1 mL, in
Turbo-Vap. Never let extracts go to dryness.
Bring the final volume to 5 mL with chloroform.
Analyze with a GC equipped with
nitrogen/phosphorus detector and DB-S capillary
column.

Date:

 

Matthew Zabik, Laboratory Director

104

QUALITY ASSURANCE

STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #: 1 By:C.Vandervoort Date: 30Apr92
7.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

7.0 Determination of Isoxaben in Grass

7.0 Extraction of Isoxaben
Preparation of Plant Samples: Bulk quantities of plant tissue should be finely
ground and thoroughly mixed to provide a homogeneous mixture.

1.

2.

3.

.U'

8.

Purification
1 .

Weigh 10 g of grass and place in gyratory shaker with 150 ml of
methanol, reagent grade. Cover and shake for one hour.

Filter the extract through a Whatrnan N o. 1

filter with a Buchner funnel with the aid of vacuum if necessary.
Return plant and filter to rotary shaker with

100 ml of methanol and shake for 0.5 hours.

Repeat step 2 with additional methanol to rinse the jar.
Transfer the extract to 1000 ml separatory

funnel. Add 75 ml of 5 % NaCl solution and 200 ml of water.
Extract with two 125 ml of glass distilled

hexane. Discard the hexane extracts.

Extract with three 75 ml of dichloromethane.

Filter the extracts through sodium sulfate with

20 ml of dichloromethane.

Evaporate the extract to dryness using rotary

vacuum evaporation at 40° C +/- 5° C.

Prepare a alumina/Florisil column for each

sample as follows:

a. Place a pledget of glass wool in the
column and tarnp it down to the bottom.

b. Add 13 ml +/- 0.5 ml of standardized
alumina and tap gently.

0. Add 5 m1+/- 0.5 ml of standardized
Florisil and tap gently.

>39)

9°

10.

11.

12.

13.

14.

105

d. Add 4 ml of anhydrous sodium sulfate, tap
gently.

Note: The alumina and Florisil must be
added to the columns in a reproducible
manner to assure a consistent elution
pattern for all samples within a set.

6. Wash column with 30 ml of dichloromethane
and discard the washings. Drain the
solvent only to the top to the column
packing.

Transfer the sample residue to the column using

two 5 ml portions of dichloromethane, allowing

each addition to pass into the absorbent.

Rinse the boiling flask with 25 ml

dichloromethane. Allow the solvent to drain to

the top of the adsorbent. Discard the eluate.

Wash the column with 50 ml of 8:2

dichloromethane/ethyl acetate. Discard the eluate.

Wash with 25 ml of 99:1 dichloromethane/methanol- . Discard

the eluate.

Add 50 ml of 99:1 dichloromethane/methanol and

collect the eluate in a 125 ml boiling flask.

Note: The solvent volumes used in steps 3, 4,

and 5 are dependent on the column profile.

Evaporate the eluate to dryness.

Add 2 ml of 2 % potassium permanganate

solution, and swirl.

Add 2 m1 of 2 M KOH, swirl.

Transfer the solution to a screw-cap vial or

test tube. Wash with 4 ml of dichloromethane

Seal and shake vigorously for 30 seconds. Let

stand for at least 5 minutes.

Remove dichloromethane layer by pipet. Filter

through anhydrous sodium sulfate into an

evaporating flask.

' Repeat steps 9-11 twice, starting with the

addition of dichloromethane.

Rinse the sodium sulfate with additional

dichloromethane, evaporate with rotary evaporator.

Dissolve the residue in 1 ml of 1:1 methanol/water mobile phase
and proceed with HPLC analysis.

106

Approved: Date:
Matthew Zabik, Laboratory Director ‘

 

107

QUALITY ASSURANCE

STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #2 1 By: Chris Vanidervoort Date: 30Apr92 A
8.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

8.0 Determination of Metalaxyl in Water

8.0 Extraction of Metalaxyl

1.

Approved:

Weigh 100 g of water and place in 250 mL

separatory funnel, add 20 g of NaCl,

solubilization.

Extract 3 time with 20 mL of methanol,.each.

time shake for three minutes and combine

extracts, then with small amount of methanol

rinse separatory ftmnel' and transfer to methanol extracts.
Reduce the volume of extracts to about almost dryness, in Turbo-
Vap.

Bring the final volume to 5 mL with methanol.

Analyze with a GC equipped with nitrogen/phosphorus detector
and DB-5 capillary column.

Date:

 

Matthew Zabik, Laboratory Director

108

QUALITY ASSURANCE
STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #: 1 By: Chris Vandervoort .Date: 07Feb92
9.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

9.0 Determination of Pr0piconazole in Water

9.0 Extraction of Propiconazole

1. Weigh a 100 g sample of water and place in a
250 mL separatory funnel, add 20 g NaCl to the sample.

2. Extract 3 times with 20 mL of dichloromethane, each time shake
for three minutes, and combine dichloromethane extracts. Rinse
separatory funnel with small amormt of dichloromethane.
Add 1 mL of iso-octane to the Turbo-Vap tube and evaporate to
< 1 mL.

3. ‘ Bring to volume with iso-octane of about 2 ml.

4. Use a N/P flame ionization detector GC.

Approved: Date:
Matthew Zabik, Laboratory Director

 

109

QUALITY ASSURANCE
STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #: 1 By: Chris Vandervoort Date: 07F eb92
10.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

10.0 Determination of Triadimefon in Water

10.0 Extraction of Triadimefon
1. Weigh a 100 g sample of water, add 100 ml of chloroform and
shake for 30 seconds. Allow the layers to separate and drain the
lower organic phase into drying flask. Repeat the extraction 2
times with portion 50 mL of chloroform and combine the '
extracts.
2. Turbo-Vap just to dryness.

Clean-up of samples
1. Prepare a Florisil column

To a 20 mm i.d. column with a glass wool pledget fill with 6:4
hexanczethyl acetate mixture. Add 10 g of 2.5 % water-
deactivated Florisil. Top with 5 g of anhydrous sodium sulfate.
Drain the solvent down to the top of the bed level of the column.
Dissolve the residue from 9.4.1.2 in 10 mL of 6:4 hexane-ethyl
acetate and transfer to the column. Adjust the flow rate to 23
drops per second. Rinse with 2 additional 10 mL of 6:4 hexane-
ethyl acetate. Eluate with additional 120 mL of the 6:4
hexane-ethyl acetate mixture and save all 150 mL of eluant.
Reduce volume in turbo-vap to dryness. Bring to volume with
hexane for GC analysis.

Approved: Date:
Matthew Zabik, Laboratory Director

 

110

QUALITY ASSURANCE
STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

 

 

Version #2 1 By: C. Vandervoort Date: 30Apr92

11.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES
11.0 Determination of Triclopyr in Grass

11.0 Extraction of Tric10pyr

l. Weigh 10 g of grass and add 6 g NaCl and one ml of 9 M H2804,
50 ml of diethyl ether, and 50-100 ml of H20 to a Erlenmeyer
flask and shake for 10 minutes. Run through a filter with
vacuum applied. Separate the aqueous from the. ether. phase.
Take the filter paper and aqueous phase and again extract with
50 ml ether. Combine the ether extracts. Wash extract with 20
ml of 10 % NaCl w/v, dry over anhydrous NaQSO4_

2. Prepare a silica-gel column by adding 3 g of silica-gel to 1 cm
i.d. column as a sluny pack with hexane. Then the column is
washed with 100 ml 129 toluene and hexane .. The residue
from step 1 is added to the column with 35:65 toluene and
hexane. The compound is eluted with 100ml 35:65 toluene and
hexane. Reduce to < 0.5 ml.

3. Esterification with BF3 in methanol by adding 0.25 ml of BF3.
Keep vial covered and at 80°C for 1 hour. Let cool then transfer

_ to a separatory funnel with 30 ml of hexane and wash extract
with 20 ml of 10 % NaCl w/v, dry over anhydrous NaQSO4_

Reduce to about 0.5 ml.
5. Analyze with electron capture detector and 30 m DB-5 capillary
column equipped GC.
Approved: Date:

 

 

Matthew Zabik, Laboratory Director

111

QUALITY ASSURANCE
STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #: 1 By: C. Vandervoort Date: 30Apr92
12.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

12.0 Determination of F lurprimidol in Grass

12.0 Extraction of F lurprimidol

1. Weigh 10 g of grass and place in 250 ml boiling
flask connected to a water-cooled reflux condensing
tube. Add 100 ml of 4:1 methanolzwater and heat to
boiling and reflux for 1 hour.

2. - Cool to room temperature and pour through a # 7
Whatrnan filter into a 250 ml separatory funnel with
30 ml of 5 % NaCl. Extract the flurprimidol with 3 x 50 ml
of hexane. Collect the hexane extract and pass through
Na2SO4. Rinse the NaQSO4 with 20 ml of hexane. Evaporate
the hexane to dryness and dissolve residue: in 32ml'of
dichloromethane.

3. Attach the Alumina B Sep-Pak cartridge (same as the Acidic
alumina) to a Sep-Pak cartridge rack. Rinse the Sep-Pak with 5
ml of dichloromethanezmethanol (3:1), followed by 10 ml of
dichloromethane. Discard the eluate. Place the sample extract
on the Sep-Pak. Rinse with 2 x 3ml of dichloromethane and
discard the eluate. Add 8 ml of dichloromethane2methanol (3:1)
and collect this fraction. Reduce to dryness and bring to volume
for the GC analysis.

4. Analyze with electron capture detector and 30 m DB-S
capillary colurrm equipped GC.

Approved: Date:
Matthew Zabik, Laboratory Director

 

112'

QUALITY ASSURANCE

STANDARD OPERATING PROCEDURES FORM

Analytical Laboratory-Pesticide Research Center

Michigan State University

Version #2 1 By: C. Vandervoort Date: 30Apr92
13.0 GENERAL LABORATORY STANDARD OPERATING PROCEDURES

13.0 Determination of 2,4-D in Grass

13.0 Extraction of 2,4-D

1.

Approved:

Weigh 10 g of grass and place in 250 ml Erlenmeyer

flask, add.5 m1 of water, 8 ml of H2504. and 50 ml

methanol and shake for 20 minutes. Filter through

Whatrnan # 1 filter. Repeat process of the filter.

The combined filtrates are reduced to the water

phase.

Extract the aqueous phase with 2 x 50 ml of dichloromethane
and reduce to about 1 ml.

Add 3 g of Florisil to a 1 cm i.d. column and t0p with about 2-4
mm of NaQSO... Rinse with 30 ml of petroleum ether and discard; ""-
Add sample to the column and follow with 15 ml of petroleum
ether and discard the eluate. Add 25 ml of 1:1 petroleum
ether2ethyl ether. Reduce volume < 0.5 ml.

Add diazomethane til yellow color remains for one hour.
Reduce volume < 0.5 m1 and bring up in volume with

hexane.

Analyze with electron capture detector and 30 m DB-5
capillary colurrm equipped GC.

Date:

 

Matthew Zabik, Laboratory Director

LIST OF REFERENCES

113

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